CN100568613C - Protected active metal electrode and battery cell structure with on-waterborne lit-par-lit structure - Google Patents

Protected active metal electrode and battery cell structure with on-waterborne lit-par-lit structure Download PDF

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CN100568613C
CN100568613C CN 200480042697 CN200480042697A CN100568613C CN 100568613 C CN100568613 C CN 100568613C CN 200480042697 CN200480042697 CN 200480042697 CN 200480042697 A CN200480042697 A CN 200480042697A CN 100568613 C CN100568613 C CN 100568613C
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battery
anode
metal
water
lithium
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CN1938895A (en
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S·J·维斯科
Y·S·尼蒙
B·D·卡茨
L·C·德永赫
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Polyplus Battery Co Inc
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Abstract

Reactive metal and reactive metal intercalation electrode structure and battery cell with ionic conduction protection structure; this ionic conduction protection structure comprises reactive metal (for example lithium) conduction impermeable stratum, and this impermeable stratum separates with electrode (anode) by the porous septum with nonaqueous electrolyte (anolyte) dipping.This protection structure has prevented the adverse effect of environment on reactive metal and another (negative electrode) side of impermeable stratum; this environment can comprise moisture or non-aqueous electrolyte (catholyte) and/or various electrochemical active material, comprises liquid, solid and gaseous oxidant.The design that safety additives also is provided and has helped making.

Description

Protected active metal electrode and battery cell structure with on-waterborne lit-par-lit structure
Background of invention
1. invention field
The present invention relates generally to the reactive metal electrochemical appliance.More particularly, the present invention relates to reactive metal (for example alkali metal, as lithium), reactive metal and embed (for example lithium-carbon, carbon) and active metal alloy (alloy or metal of alloying (for example tin) electrochemistry (for example electrode) structure and the battery cell of lithium-Xi) for example.Electrode structure has ionic conduction protection structure, and this protection structure comprises reactive metal (for example lithium) conduction impermeable stratum, and it is separated by porous septum and the electrode (anode) with the nonaqueous electrolyte dipping.This protection structure has prevented the adverse reaction of environment on another (negative electrode) side of reactive metal and impermeable stratum, and that environment can comprise is moisture, air or liquid organic electrolyte and/or electrochemical active material.
2. description of Related Art
The low equivalent of alkali metal such as lithium makes them especially attractive as the battery electrode parts.Lithium can provide the energy of the every volume bigger than conventional batteries standard-nickel and cadmium.Unfortunately, rechargeable lithium metal battery also not success on market.
The failure of rechargeable lithium metal battery is to a great extent owing to the battery circulatory problems.In charging and discharge cycles repeatedly, lithium " dendrite " grows out from metal lithium electrode gradually by electrolyte, and final contact is anodal.This causes internal short-circuit of battery, and battery just can not be re-used after less circulation several times.In circulation, lithium electrode also may grow " spongy " deposit that meeting is removed from negative pole, and has therefore reduced battery capacity.
In order to solve the cycle performance of lithium difference in liquid electrolytic plastidome, some researchers propose cathode of lithium is applied " protective layer " towards electrolytical side.This protective layer must can conductive lithium ion, but prevent contact between lithium electrode surface and the main body electrolyte simultaneously.The technology of many application protective layers does not all have successfully.
The lithium coat of metal of some expections all forms by the reaction between the compound in the cell electrolyte of lithium metal and contact lithium in position.Major part in these in-situ films all is to grow by the control chemical reaction after the assembled battery.Usually, this film has and allows the porous form of part electrolyte osmosis to the naked lithium metal surface.Therefore, they can not protect lithium electrode fully.
The various lithium protective layers that are shaped have in advance also been considered.For example, United States Patent (USP) 5314765 (being signed and issued to Bates on May 24th, 1994) has been described the exterior technology of the lithium electrode of making the oxynitride phosphor lithium (" LiPON ") that comprises the skim sputter or associated materials.LiPON is a kind of glassy state single ion conductor (a conductive lithium ion), it has been studied the possible electrolyte as solid-state lithium micro cell, solid-state lithium micro cell is fabricated on the silicon and is used for power integrated circuit (referring to United States Patent (USP) 5597660,5567210,5338625 and 5512147, all being signed and issued to Bates etc.).
The technology of using glassy state or amorphous state protective layer such as LiPON in the reactive metal battery electrode has been developed in work in the applicant laboratory.(sign and issue referring to for example United States Patent (USP) 6025094,02/15/00,6402795,06/11/02 sign and issue, and 6214061,04/10/01 sign and issue and 6413284,07/02/02 sign and issue, and all transfer PolyPlus Battery company).
In aqueous environment, use the existing effort of lithium anode to rely on the corrosion that is used for slowing down the Li electrode that makes of the use of strong alkaline condition such as the dense KOH aqueous solution, or rely on and use polymer coating to stop water to be diffused on the Li electrode surface on the Li electrode.But, in all cases, all have the reaction of a large amount of alkali metal electrode and water.To this, it is impossible that the prior art instruction is used moisture negative electrode or electrolyte with the Li-metal anode, because the puncture voltage of water is about 1.2V, the Li/ water battery can have the voltage of about 3.0V.Direct contact between the lithium metal and the aqueous solution causes the reaction of strong parasitic chemical and without any the corrosion of the lithium electrode of useful purpose.Therefore, the research focus in the lithium metal battery field is directly in the exploitation of effective non-water (major part is organic) electrolyte system.
Summary of the invention
The present invention relates generally to the reactive metal electrochemical appliance.More particularly, the present invention relates to reactive metal (for example alkali metal, as lithium), reactive metal and embed (for example lithium-carbon, carbon) and active metal alloy (alloy or metal of alloying (for example tin) electrochemistry (for example electrode) structure and the battery cell of lithium-Xi) for example.Electrode structure has the protection structure of ionic conduction, and this protection structure comprises the basic impermeable stratum of reactive metal (for example lithium) ionic conduction, and it is separated by porous septum and the electrode (anode) with nonaqueous electrolyte (anolyte) dipping.This protection structure has prevented the adverse reaction of environment on another (negative electrode) side of reactive metal and impermeable stratum, and that environment can comprise is moisture, air or liquid organic electrolyte (catholyte) and/or electrochemical active material.
The membrane layer (intermediate layer) of protection structure prevents that the reactive metal (for example lithium) of anode and active metallic ion from conducting electricity adverse reaction between the basic impermeable stratum.Therefore, this structure has been isolated (separation) effectively anode/anolyte and solvent, electrolyte treatment and/or cathode environment, comprise common this environment, and allow ion transport to enter and leave the environment that these may corrode simultaneously Li or other reactive metal deep-etching.
The various embodiments of battery of the present invention and battery structure comprise that reactive metal, active metallic ion, active metal alloy metal and reactive metal embed anode material, and these materials are had the ionic conduction protection structure of non-water anolyte and protect.These anodes can combine with various possible cathode systems in battery cell, and cathode systems comprises water, air, metal hydride and metal oxide cathode and relevant catholyte liquid system, especially moisture catholyte liquid system.
Break or otherwise broken and allow the aggressivity catholyte to enter and, also can in structure of the present invention and battery, introduce safety additives for the basic impermeable stratum (for example glass or glass-ceramic film) of protection structure near the situation of lithium electrode.The on-waterborne interstratified structure can mix can cause the gel/polymerizer that forms impermeable polymer on the lithium surface when contacting with reactive cathodes electrolyte.For example, anolyte can be included in the insoluble or monomer of dissolved polymers seldom in the water, dioxolanes (Diox)/poly-dioxolanes (polydioxaloane) for example, and catholyte can comprise monomer polymerization initiator, for example Bronsted acid.
In addition, structure of the present invention and battery can adopt any suitable form.A kind of favourable form that helps making is a tubular form.
In one aspect, the present invention relates to Electrochemcial cell structures.This structure comprises the anode of being made up of reactive metal, active metallic ion, active metal alloy, active metal alloy metal or reactive metal insert material.Anode has ionic conduction protection structure on its surface.This structure comprises having non-water anolyte and compatible with reactive metal chemistry and contact the active metallic ion conductive diaphragm layer of anode, with chemical compatible and contact the waterproof substantially ion conductive layer of membrane layer with membrane layer and aqueous environment.Membrane layer can be the pellicle with organic anolyte dipping, for example the microporous polymer that floods with liquid or gel phase anolyte.This electrochemistry (electrode) structure can comprise that moisture cathode systems pairing forms according to battery cell of the present invention with cathode systems.
Structure of the present invention and can have various structures (comprising prism-shaped and cylindric) and form in conjunction with the battery cell of structure of the present invention, comprise active metallic ion, alloy and embedding anode, moisture, water, air, metal hydride and metal oxide cathode and moisture, organic or ionic liquid catholyte; Strengthen electrolyte (anolyte and/or the catholyte) group and the thing of battery security and/or performance; And manufacturing technology.
Further describe and enumerate these and other feature of the present invention in the detailed description hereinafter.
The accompanying drawing summary
Fig. 1 is the schematic diagram that combines according to the electrochemical structure battery of ionic conduction protection of the present invention intermediate layer structure.
Fig. 2 is the schematic diagram that combines according to the battery cell of ionic conduction protection of the present invention intermediate layer structure.
Fig. 3 A-C illustrates the embodiment according to the battery cell of use tubulose protection anode design of the present invention.
The properties data figure of Fig. 4-7 various batteries of ionic conduction protection of the present invention intermediate layer structure for diagram combines.
Fig. 8 illustrates the test cell at the various Li paper tinsel thickness of aqueous electrolyte test that are used for producing data shown in Figure 7.
Fig. 9 is that the battery specific energy that combines the anode of the ionic conduction of the present invention protection intermediate layer structure with different-thickness infers that curve, Li thickness are the battery weight specific energy values of protection anode of 3.3mm and battery structure diagram and the parameter of calculating usefulness.
Figure 10 illustrates according to Li/ water battery of one embodiment of this invention and fuel cell hydrogen generator.
Specific embodiments describes in detail
To describe in detail specific embodiments of the present invention now.The example of specific embodiments is illustrated in the drawings.Although described the present invention, will be appreciated that to be not intended to limit the present invention this specific embodiments in conjunction with these specific embodiments.On the contrary, be intended to cover replacement scheme, improvement and the equivalent that comprises in the spirit and scope of the present invention that limit as accessory claim.In the following description, in order to provide a large amount of details have been set forth in thorough understanding of the present invention.Partly or entirely these details can not implemented the present invention yet.In other cases, fuzzy in order to make the present invention necessarily, do not describe well-known process operation in detail.
When using in conjunction with " comprising ", " a kind of method comprises ", " a kind of device comprises " or similar language throughout in this specification and accessory claim, singulative " " and " being somebody's turn to do " comprise plural reference, unless clearly indicate in addition in the literary composition.Unless otherwise defined, whole technology used herein has and the identical implication of the conventional understanding of general technical staff of the technical field of the invention with scientific terminology.
Foreword
Reactive metal is reactive high under ambient air conditions, and can be benefited from the barrier layer as electrode the time.They are generally alkali metal as (for example lithium, sodium or potassium), alkaline-earth metal (for example calcium or magnesium), and/or some transition metal (for example zinc), and/or two or more alloy in these.Can use following reactive metal: alkali metal (for example Li, Na, K), alkaline-earth metal (for example Ca, Mg, Ba) or with binary or the ternary alkali metal alloy of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In.Preferred alloy comprises lithium-aluminium alloy, lithium silicon alloy, lithium-tin alloy, lithium silver alloy and sodium lead alloy (Na for example 4Pb).Preferred active metal electrode is made of lithium.
The low equivalent of alkali metal such as lithium makes them especially attractive as the battery electrode composition.Lithium can provide than conventional batteries standard-nickel and the bigger unit volume energy of cadmium.But, the lithium metal or in conjunction with lithium, electromotive force is near the compound of lithium metal electromotive force (for example in about 1 volt), as lithium alloy and lithium-ion (lithium embedding) anode material, many potential attractive electrolyte and cathode material had high reactivity.The invention describes the cathode side that uses the nonaqueous electrolyte intermediate layer to construct to isolate reactive metal (for example alkali metal, as lithium), active metal alloy or active metallic ion electrode (the normally anode of battery cell) and surrounding environment and/or battery.This structure comprises and has non-water anolyte the active metallic ion conductive diaphragm layer of (i.e. electrolyte around anode), this membrane layer and reactive metal chemistry is compatible and contact anode, also comprises chemical compatible and contact the waterproof substantially ion conductive layer of membrane layer with membrane layer and aqueous environment.Nonaqueous electrolyte intermediate layer structure has been isolated (separation) effectively anode and surrounding environment and/or negative electrode, comprise catholyte (i.e. electrolyte around negative electrode) environment, comprise common this environment, and allow ion transport to enter and leave the environment that these may corrode simultaneously Li or other reactive metal deep-etching.In this manner, other parts of permission electrochemical appliance such as battery cell are made with this structure big flexibility ratio are just arranged.Anode is used in combination almost any solvent, electrolyte and/or cathode material with the isolation permission of other parts of battery pack or other electrochemical cell in this manner with anode.And, the optimization of electrolyte or cathode side dicyandiamide solution can be carried out, and anode stability or performance can be do not influenced.
Have many can be from having reactive metal (alkali metal for example, lithium for example) cell cathode side or the reactive metal in the battery cell embed and use the application that is benefited in the aqueous solution, air and other material on (for example lithium alloy or lithium-ion) anode, the aqueous solution comprises water and aqueous electrolyte, other material comprises organic solvent/electrolyte and ionic liquid to lithium and other responding property of reactive metal.
Use embedding lithium electrode material such as lithium-carbon and lithium alloy anode rather than lithium metal to be used for anode and also can provide useful battery behavior.At first, allow to realize the battery cycle life that prolongs and do not have to form the risk that can cause the lithium metallic dendrite of film damage to the film surface from the Li superficial growth.And, in some embodiments of the present invention, use lithium-carbon and lithium alloy anode to replace lithium anodes can significantly improve battery security, because this has been avoided the formation of strong reactivity " spongy " lithium in the cyclic process.
The invention describes protected active metal, alloy or intercalation electrode, it makes very that the lithium battery of high-energy-density becomes possibility, as use otherwise with for example lithium metal rise the aqueous electrolyte of adverse effect or other electrolytical those.The right example of these high energy batteries has lithium-air, lithium-water, lithium-metal hydride, lithium-metal oxide and these lithium alloy and lithium-ion variant.Battery of the present invention can mix other component strengthening battery security in their electrolyte (anolyte and catholyte), and can have various structures, comprises plane and tubulose/cylindric.
The on-waterborne lit-par-lit structure
On-waterborne lit-par-lit structure of the present invention is located in the Electrochemcial cell structures; this structure has anode and the protection of the ionic conduction on anode first surface structure, and anode is made of the material that is selected from reactive metal, active metallic ion, active metal alloy, active metal alloyization and the reactive metal insert material.This structure is made of active metallic ion conductive diaphragm layer with non-water anolyte and fluid-tight substantially ion conductive layer, membrane layer and reactive metal chemistry is compatible and contact anode, and ion conductive layer and membrane layer and aqueous environment are chemical compatible and contact membrane layer.Membrane layer can comprise pellicle, and for example with the microporous polymer of organic anolyte dipping, microporous polymer is as can be from Celgard, Inc.Charlotte, and North Carolina obtains.
Protection of the present invention structure combines the basic impermeable stratum of active metallic ion electro-conductive glass or glass-ceramic (for example lithium ion conducting glass-ceramic (LIC-GC)), its have high active metallic ion conductivity and to can with the aggressivity electrolyte of the lithium metal kickback stability of aqueous electrolyte for example.Suitable material be fluid-tight substantially, ionic conduction and with aqueous electrolyte or otherwise compatible with other electrolyte (catholyte) and/or the cathode material chemistry of for example lithium metal adverse effect.This glass or glass-ceramic material do not have substantially the gap, can not swelling and be ionic conduction in essence.That is to say that they do not rely on the existence of liquid electrolyte or other reagent owing to their ionic conductivities own.They also have high ionic conductivity, at least 10 -7S/cm, usually at least 10 -6S/cm, for example at least 10 - 5S/cm-10 -4S/cm, and high to 10 -3S/cm or higher, thus total ionic conductivity of multilayer protection structure is at least 10 -7S/cm, and high to 10 -3S/cm or higher.The thickness of this layer is preferably about 0.1-1000 micron, and perhaps the ionic conductivity when this layer is about 10 -7During S/cm, be about 0.25-1 micron, or when the layer ionic conductivity about 10 -4With about 10 -3In the time of between the S/cm, be about 10-1000 micron, preferably between 1 and 500 micron, more preferably between 10 and 100 microns, for example 20 microns.
The suitable example of suitable waterproof substantially lithium ion conducting layer comprises glassy state or amorphous metal ion conductor, as phosphorus base glass, oxide-based glasses, phosphorus-oxynitride base glass, the basic glass of sulphur (sulpher), oxide/sulfide base glass, selenides base glass, gallium base glass, germanium base glass or boracite glass (as D.P.Button etc. at Solid State Ionics, the 9-10 volume, part 1 is described among the 585-592 (December nineteen eighty-three)); Pottery active metallic ion conductor is as lithium beta-alumina, sodium beta-alumina, Li superionic conductors (LISICON), Na superionic conductors (NASICON) etc.; Or glass-ceramic active metallic ion conductor.Object lesson comprises LiPON, Li 3PO 4.Li 2S.SiS 2, Li 2S.GeS 2.Ga 2S 3, Li 2O11Al 2O 3, Na 2O11Al 2O 3, (Na, Li) 1+xTi 2-xAl x(PO 4) 3(0.6≤x≤0.9) and crystallography dependency structure, Na 3Zr 2Si 2PO 12, Li 3Zr 2Si 2PO 12, Na 5ZrP 3O 12, Na 5TiP 3O 12, Na 3Fe 2P 3O 12, Na 4NbP 3O 12, Li 5ZrP 3O 12, Li 5TiP 3O 12, Li 3Fe 2P 3O 12And Li 4NbP 3O 12And their combination, randomly be sintered or melt.Suitable ceramic ion activity metal ion conductor is described in the United States Patent (USP) 4985317 of Adachi etc. for example, and this paper is incorporated herein by reference in full and is used for various purposes.
The especially suitable glass-ceramic material of basic impermeable stratum that is used to protect structure is for having following composition and comprising by Li 1+x(M, Al, Ga) x(Ge 1-yTi y) 2-x(PO 4) 3And/or Li 1+x+yQ xTi 2- xSi yP 3-yO 12The lithium ion conducting glass-ceramic of the principal crystalline phase that constitutes:
Figure C20048004269700161
Li wherein 1+x(M, Al, Ga) x(Ge 1-yTi y) 2-x(PO 4) 3Middle X≤0.8 and 0≤Y≤1.0, M is the element that is selected from Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, Li 1+x+yQ xTi 2-xSi yP 3-yO 12In 0＜X≤0.4 and 0＜Y≤0.6, Q is Al or Ga.By raw material being fused into melt, melt being cast into glass and glass heat-treated and obtain glass-ceramic.This material can obtain from Japanese OHARA company, and further is described in United States Patent (USP) 5702995,6030909,6315881 and 6485622, and this paper is incorporated herein by reference.
The basic impermeable stratum of this lithium ion conducting and their manufacturing technology and the combination in battery cell are described among the U.S. Provisional Patent Application No.60/418899, this patent was submitted on October 15th, 2002, exercise question is IONICALLY CONDUCTIVE COMPOSITESFOR PROTECTION OF ANODES AND ELECTROLYTES, its corresponding U.S. Patent application is No.10/686189 (Attorney Docket No.PLUSP027), on October 14th, 2003 submitted to, exercise question is IONICALLY CONDUCTIVE COMPOSITESFOR PROTECTION OF ACTIVE METAL ANODES, U.S. Patent application No.10/731771 (Attorney Docket No.PLUSP027X1), on December 5th, 2003 submitted to, exercise question is IONICALLY CONDUCTIVE COMPOSITES FORPROTECTION OF ACTIVE METAL ANODES, with U.S. Patent application No.10/772228 (Attorney Docket No.PLUSP039), on February 3rd, 2004 submitted to, and exercise question is IONICALLY CONDUCTIVE MEMBRANES FORPROTECTION OF ACTIVE METAL ANODES AND BATTERYCELLS.Introduce these applies for reference to this paper in full for various purposes.
Critical when using these strong electro-conductive glass and glass-ceramic in lithium (or other reactive metal or reactive metal embed) battery is limited in them to lithium metal or the electromotive force reactivity in conjunction with the compound of lithium near lithium metal electromotive force (for example in about 1 volt).Nonaqueous electrolyte of the present invention intermediate layer isolates lithium (for example) electrode and glass or glass-ceramic film reaction.The on-waterborne interbed can have pellicle, as the Celgard micro-pore septum, prevents that the lithium electrode Mechanical Contact is on glass or glass-ceramic film.Flood this film with the liquid organic electrolyte that has solvent (anolyte), solvent such as ethylene carbonate (EC), propylene carbonate (PC), 1,2-dimethoxy-ethane (DME), 1,3-dioxolanes (DIOX), or various ether, glyme, lactone, sulfone, sulfolane or their mixture.It may also or alternatively have polymer dielectric, gel-type electrolyte or these combination.Important criterion is that lithium electrode is stable in non-water anolyte, and non-water anolyte fully conducts the Li+ ion, and lithium electrode does not directly contact glass or glass-ceramic film, and whole device allows lithium ion to pass glass or glass-ceramic film.
With reference to figure 1, illustrate and described a specific embodiments of the present invention.Fig. 1 has shown out-of-proportion figure of Electrochemcial cell structures 100, and Electrochemcial cell structures 100 has reactive metal, active metallic ion, active metal alloy metal or reactive metal insert material anode 102 and ionic conduction protection structure 104.Protect structure 104 to have and on the surface of anode 102, have non-water anolyte the active metallic ion conductive diaphragm layer 106 and the waterproof substantially ion conductive layer 108 that contacts membrane layer 106 of (also be called sometimes and shift electrolyte).Membrane layer 106 is compatible with the reactive metal chemistry, and basic impermeable stratum 108 is compatible with the aqueous environment chemistry with membrane layer 106.Structure 100 can randomly comprise current-collector 110, and current-collector 110 is made up of the suitable conducting metal that can not form alloy with reactive metal or embed reactive metal.When reactive metal was lithium, suitable collector materials was a copper.Current-collector 110 also can be used for sealing anode and surrounding environment is isolated to prevent the adverse effect of reactive metal and surrounding air or moisture.
Membrane layer 106 is made of the pellicle with organic anolyte dipping.For example, this pellicle can be microporous polymer, and as can be from Celgard, Inc obtains.Organic anolyte can be liquid phase or gel phase.For example, anolyte can comprise the solvent that is selected from organic carbonate, ether, lactone, the sulfone etc. and their combination, as EC, PC, DEC, DMC, EMC, 1, and 2-DME or senior glyme, THF, 2MeTHF, sulfolane and their combination.1, the 3-dioxolanes also can be used as the anolyte solvent, especially but must not be the fail safe that is used to strengthen in conjunction with the battery of this structure the time, as hereinafter further describing.When anode electrode liquid is in gel phase, can add gelling agent such as Kynoar (PVdF) compound, hexafluoropropylene-Ya vinylidiene fluoride copolymer (PVdf-HFP), polyacrylonitrile compound, crosslinked polyethers compound, polyoxyalkylene compounds, polyoxyethylene ene compound and combination etc. so that solvent forms gel.Certainly, suitable anolyte also comprises active metal salt, as under the situation of lithium, and LiPF for example 6, LiBF 4, LiAsF 6, LiSO 3CF 3Or LiN (SO 2C 2F 5) 2An example of suitable membrane layer is the 1M LiPF6 that is dissolved in the propylene carbonate, and is immersed in the Celgard microporous polymer membranes.
Protection according to the present invention is configured with dramatic benefit.Especially the battery structure that combines this structure is easier to make.In an example, against placing with the micro-pore septum of organic liquid or gel electrolyte dipping, barrier film is then near glass/glass pottery active metallic ion conductor by simply for the lithium metal.
When using glass-ceramic, realized other advantage of on-waterborne interbed.When the amorphous glass of the above-cited OHARA type that house journal is described of heat treatment, the glass devitrification causes the formation of glass-ceramic.But this heat treatment can cause the formation of surface roughness, and this is difficult to utilize inorganic protection intermediate layer such as LiPON, Cu 3The vapour deposition of N etc. applies.The use in liquid (or gel) nonaqueous electrolyte intermediate layer can be easily covers this rough surface by conventional liquid stream, thereby has eliminated the needs to surface finish etc.In this sense, but operation technique is as " contraction " ((T.Kessler as described in Sony company and the Shott Glass, H.Wegener, T.Togawa, M.Hayashi and T.Kakizaki, " Large MicrosheetGlass for 40-in.Class PALC Displays ", 1997, FMC2-3, from Shott Glass website: http://www.schott.com/english downloads, this paper is incorporated herein by reference)) form thin glassy layer (20-100 micron), and these glass of heat treatment form glass-ceramic.
Battery cell
The on-waterborne lit-par-lit structure is adopted in battery cell usually effectively.For example, the electrochemical structure 100 of Fig. 1 can form battery 200 with cathode systems 120 pairings, as shown in Figure 2.Cathode systems 120 comprises electron conduction parts, ionic conduction parts and electro-chemical activity parts.Because the isolation that the protection structure provides, cathode systems 120 can have any required composition, is not subjected to anode or anolyte to form restriction.Especially, cathode systems can be introduced in other cases the component with anode reactive metal kickback, as hydrous material, comprises water, moisture catholyte and air, metal hydride cell and metal oxide electrode.
In one embodiment, the Celgard barrier film will be sidelong against one of thin glass-ceramic and be put, and be non-water liquid or gel electrolyte then, be lithium electrode again.At the opposite side of glass ceramic film, can use the aggressivity solvent, as aqueous electrolyte.In this manner, can make up for example cheap Li/ water or Li/ air cell.
Can have very high capacity and specific energy according to battery of the present invention.For example, capacity is greater than 5, greater than 10, greater than 100 or even greater than 500mAh/cm 2Battery all be possible.As the following examples further as described in, confirmed that the thick Li/ water test battery of the present invention of the about 3.35mm of Li anode has about 650mAh/cm 2Capacity.Based on this performance, infer the very high specific energy that demonstrates Li/ air cell of the present invention.For example, for have the thick Li anode of 3.3mm, laminated thickness is that 6mm and area are 45cm 2The Li/ air cell, Feng Zhuan specific energy is not about 3400Wh/l (4100Wh/kg), the specific energy of encapsulation is about 1000Wh/l (1200Wh/kg), supposes 70% encapsulation load.
Cathode systems
As mentioned above, because the isolation that protection structure provides, can have any required composition, not be subjected to anode or anolyte to form restriction according to the cathode systems 120 of battery cell of the present invention.Especially, cathode systems can be introduced in other cases the component with anode reactive metal kickback, as hydrous material, comprises water, the aqueous solution and air, metal hydride cell and metal oxide electrode.
Battery cell of the present invention can include, without being limited to water, the aqueous solution, air electrode and metal hydride cell, be described in the common co-pending application No.10/772157 of ACTIVE METAL/AQUEOUSELECTROCHEMICAL CELLS AND SYSTEMS as exercise question, this paper is incorporated herein by reference in full and is used for various purposes, and metal oxide electrode, for example employed in conventional lithium ion battery.
Huge flexibility ratio during anode that obtains by protection of the present invention intermediate layer structure and the effective isolation between the negative electrode can also make cathode systems especially Aquo System and non-aqueous system are selected becomes possibility.Because protected anode separates fully with catholyte, thereby the compatibility of catholyte and anode no longer is problem, can use unsettled solvent and salt on the Li dynamics.
For the battery that makes water as the electro-chemical activity cathode material, porous electron conduction supporting construction can provide the electron conduction parts of cathode systems.Aqueous electrolyte (catholyte) provides the ionophore of Li ion transport (conductivity) and the anion that combines with Li.Electro-chemical activity component (water) and ionic conduction component (moisture catholyte) will be blended into single solution, although they conceptive be the individual component of battery cell.The suitable catholyte of Li/ water battery Battery pack of the present invention comprises any aqueous electrolyte with appropriate ions conductivity.Suitable electrolyte can be acidity, for example strong acid such as HCl, H 2SO 4, H 3PO 4Or weak acid such as acetate/lithium acetate; Alkalescence, for example LiOH; Neutrality, for example seawater, LiCl, LiBr, LiI; Or both sexes, for example NH 4Cl, NH 4Br etc.
Seawater makes the battery cell of using with Yu Haiyang with unusual high-energy-density become possibility as electrolytical suitability.Before the use, battery structure is made up of protected anode and porous electron conduction supporting construction (the electron conduction parts of negative electrode).When needs,, this battery finishes battery by being immersed in the seawater that electro-chemical activity and ionic conduction parts can be provided.Because back one parts are provided by the seawater in the environment, a part that therefore is not used as battery cell before it uses betransported (thereby not needing to be included in the energy content of battery density calculation).This battery is called as " open circuit " battery, because do not comprise the product on the cathode side.Therefore, this battery is a primary cell.
According to the present invention, secondary Li/ water battery also is possible.As mentioned above, this battery is called as " closed circuit " battery, because comprise the product on the cathode side on the cathode side of battery, it is used for suitable move the Li ion and returning for anode and recharge by striding across diaphragm when recharging electromotive force in that battery is applied.
Explanation and hereinafter further described as mentioned in another embodiment of the present invention, is coated in ionomer on the porous catalytic electron conduction carrier and has reduced or eliminated needs to electrochemical active material intermediate ion conductivity.
The electrochemical reaction that takes place in the Li/ water battery is a redox reaction, and wherein the electro-chemical activity cathode material obtains reduction.In the Li/ water battery, catalysis electron conduction carrier helps redox reaction.As mentioned above, but be not restricted to this, in the Li/ water battery, this cell reaction is considered to:
Li+H 2O＝LiOH+1/2H 2
The half-cell reaction at anode and negative electrode place is considered to:
Anode: Li=Li ++ e -
Negative electrode: e -+ H 2O=OH -+ 1/2H 2
Therefore, the catalyst of Li/ water negative electrode has promoted the electron transfer to water, produces hydrogen and hydroxide ion.The cheap catalyst commonly used that is used for this reaction is the nickel metal; Noble metal such as Pt, Pd, Ru, Au etc. also work but are expensive.
Battery with protected Li anode and aqueous electrolyte also is considered in the scope of Li of the present invention (or other reactive metal)/water battery, and wherein aqueous electrolyte is made up of the gaseous state and/or the solid oxide agent that can be used as active cathode material (electro-chemical activity component) that may be dissolved in the water.Use as the water soluble compound of the oxidant stronger than water in some applications with lithium/water battery mutually specific energy significantly increase the energy content of battery, wherein in the battery discharge reaction, at the cathode surface place electrochemical hydrogen takes place and separates out.The example of this gaseous oxidizer has O 2, SO 2And NO 2In addition, metal nitrite NaNO especially 2And KNO 2With metal sulphite such as Na 2SO 3And K 2SO 3All be the oxidant stronger than water, and can be easily with big concentration dissolving.Water-soluble another kind of inorganic oxidizer is the peroxide of lithium, sodium and potassium, and hydrogen peroxide H 2O 2
Use hydrogen peroxide especially favourable as oxidant.At least two kinds of methods of using hydrogen peroxide are arranged in battery cell according to the present invention.At first, the chemical breakdown of hydrogen peroxide causes the generation of oxygen on the cathode surface, and oxygen can be used as active cathode material.Secondly, more efficient methods perhaps is based on the direct electroreduction of hydrogen peroxide on the cathode surface.On the principle, hydrogen peroxide can be reduced from alkalescence or acid solution.For the battery of the hydrogen-peroxide reduction that utilizes acid solution, can obtain the highest energy density.In this case, the E right with Li/ water 0=3.05V compares, and the battery with Li anode produces E 0=4.82V (reference condition).But because two kinds of acid and hydrogen peroxide be not to protecting the very high reactivity of Li, this battery in fact only could be realized for the protected Li anode such as this class according to the present invention.
For the battery that uses air as the electro-chemical activity cathode material, the air electrochemical active component of these batteries is included as the moisture that electrochemical reaction provides water.Battery has the electron conduction supporting construction that is electrically connected with anode to allow electron transfer to come the reducing atmosphere active material of cathode.The electron conduction supporting construction is porous normally, with the reduction that allows fluid (air) to flow and catalytic is arranged or come the catalytic cathode active material with catalyst treatment.Aqueous electrolyte or ionomer with appropriate ions conductivity also contact with the electron conduction supporting construction, finish redox reaction to allow the ion transport in the electron conduction supporting construction.
The air cathode system comprises electron conduction parts (for example porous electronic conductor), have the ionic conduction parts of at least a aqueous ingredients and as the air of electro-chemical activity parts.It can be any suitable air electrode, is included in those that use always in metal (for example Zn)/air cell or low temperature (for example PEM) fuel cell.The air cathode that uses in metal/air battery especially Zn/ air cell is described in many sources, comprise " Handbook of Batteries " (Linden and T.B.Reddy, McGraw-Hill, NY, the third edition), and by which floor form usually, comprise air diffusion membrane, hydrophobic Teflon layer, catalyst layer and metal electron conductive component/current-collector, sieve as Ni.Catalyst layer also comprises and can be water-based and/or from poly-ionic conduction component/electrolyte.Typical aqueous electrolyte is made up of the KOH that is dissolved in the water.Typically form by hydration (water) Li ionic conductive polymer such as perfluorinated sulfonic acid polymer film (for example du Pont NAFION) from polyelectrolyte.Air diffusion membrane is regulated air (oxygen) stream.Hydrophobic layer stops the electrolyte osmosis of battery in air diffusion membrane.This layer comprises carbon and Teflon particle usually.Catalyst layer comprises high surface area carbon usually and quickens the catalyst of oxygen reduction.In most of commercial negative electrodes, use metal oxide such as MnO 2Catalyst as oxygen reduction.The catalyst that substitutes comprises Metallomacrocycle such as cobalt phthalocyanine and high dispersive noble metal such as platinum and platinum/ruthenium alloy.Because air electrode structure and active metal electrode chemical isolation, so the chemical composition of air electrode is not subjected to the reactive restriction possible with active material of positive electrode.This allows to use the more high performance air electrode of material design that can corrode not protected metal electrode usually.
Reactive metal/moisture battery cell according to protected anode of combining of another type of the present invention and cathode systems is lithium (or other reactive metal)/metal hydride battery.For example, the lithium anode with on-waterborne lit-par-lit structure protection described herein can be discharged in the electrolytical aqueous solution in being suitable as lithium/metal hydride battery and be charged.Suitable electrolyte provides source or proton.Example comprises halide acid or acid salt, comprises chloride or bromide acid or salt for example HCl, HBr, NH 4Cl or NH 4The aqueous solution of Br.
Except systems such as above-mentioned moisture, air, utilize to combine the performance that conventional Li-ion battery negative electrode and electrolytical cathode systems can be improved negative electrode such as metal oxide cathode (Li for example xCoO 2, Li xNiO 2, Li xMn 2O 4And LiFePO 4) and binary, ternary or the multicomponent mixture of alkyl carbonate, or they and as Li slaine (LiPF for example 6, LiAsF 6Or LiBF 4) the mixture of ether of solvent; Or Li metal battery negative electrode (for example elementary sulfur or polysulfide) and electrolyte, this electrolyte is by organic carbonate, ether, glyme, lactone, sulfone, sulfolane and their combination, as EC, PC, DEC, DMC, EMC, 1, constituting of 2-DME, THF, 2MeTHF and they, described in for example United States Patent (USP) 6376123, this paper is incorporated herein by reference.
In addition, catholyte solution can only be made up of low viscosity solvent, as ether, picture 1,2-dimethoxy-ethane (DME), oxolane (THF), 2-methyltetrahydrofuran, 1,3-dioxolanes (DIOX), 4-methyl dioxolanes (4-MeDIOX) or organic carbonate such as dimethyl carbonate (DMC), carbonic acid ethyl methyl esters (EMC), diethyl carbonate (DEC) or their mixture.In addition, can use ester solvent or cosolvent such as the methyl formate and the methyl acetate of ultra-low viscosity, they have very high reactivity to unprotected Li.Those skilled in the art know that ionic conductivity and diffusion velocity and viscosity are inversely proportional to, to such an extent as in whiles such as whole other situations, battery performance improves when solvent viscosity reduces.The use of this catholyte dicyandiamide solution has significantly improved battery performance, discharge especially at low temperatures and charge characteristic.
In catholyte of the present invention, also can use ionic liquid.To be fusing point at 100 degree following, frequent even be lower than the organic salt of room temperature for ionic liquid.The most frequently used ionic liquid is imidazoles and pyridine derivate, and phosphine or tetraalkyl ammonium compound also are known.Ionic liquid has desirable high ionic conductivity, high thermal stability, no measurable vapour pressure and low flammability attribute.Representational ionic liquid has 1-ethyl-3-methylimidazole toluene fulfonate (EMIM-Ts), 1-butyl-3-methylimidazole octyl sulfate (BMIM-OctSO4), 1-ethyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methyl imidazolium tetrafluoroborate.Although the ionic liquid that is used for electrochemical applications such as capacitor and battery is had great interest, they are unsettled to lithium metal and lithiated carbon.But protected lithium anode described in the present invention and direct chemical reaction are isolated, and therefore use ion liquid lithium metal battery to can be used as a kind of embodiment of the present invention.This battery should be at high temperature stable especially.
Safety additives
As safety measure, the on-waterborne lit-par-lit structure can be combined in reactive electrolyte (for example water) can cause gel/polymerizer that impermeable polymer forms on anode (for example lithium) surface when contacting.Thereby this safety measure is used to protect the basic impermeable stratum (for example glass or glass-ceramic film) of structure breaks or otherwise damage and allow the aggressivity catholyte to enter and arrive the situation that lithium electrode has increased kickback possibility between Li anode and the moisture catholyte.
By in anolyte, provide be insoluble to or seldom water-soluble polymer monomer for example dioxolanes (Diox) (for example quantity is about 5-20 volume %) and in catholyte, provide monomer with polymerization initiator for example Bronsted acid prevent this reaction.Diox base anolyte can be by organic carbonate (EC, PC, DEC, DMC, EMC), ether (1,2-DME, THF, 2MeTHF, 1,3-dioxolanes and some other) and their mixture composition.Comprise that dioxolanes is as primary solvent (for example 50-100 volume %) and Li salt especially LiAsF 6, LiBF 4, LiSO 3CF 3, LiN (SO 2C 2F 5) 2Anolyte especially attractive.Diox is the well passivated agent on Li surface, has obtained the good circulation data (referring to for example United States Patent (USP) 5506068) of Li metal in the Diox base electrolyte.Except the compatibility of it and Li metal, the Diox that combines with above-mentioned ion salt forms strong conducting electrolyte.Corresponding moisture catholyte comprises the Diox polymerization initiator that can produce water insoluble or only water-soluble on a small quantity Diox polymerizate (poly-dioxolanes).
If film damages, the catholyte that then comprises the initator of dissolving directly contacts with Diox base anolyte, and the polymerization of Diox takes place against the Li anode surface.Poly-dioxolanes is the Diox polymerized product, has high resistance, thereby battery quits work.In addition, the poly-dioxolanes layer of formation is as stoping the barrier layer of reacting between Li surface and the moisture catholyte.Diox can be dissolved in the Bronsted acid polymerization in the catholyte.And water miscible lewis acid especially benzo benzoyl (benbenzoyl) cation can be used for this purpose.
Therefore, by using basic anolyte of dioxolanes (Diox) and the catholyte that comprises the Diox polymerization initiator can realize the raising of circulation ability and fail safe.
Active metallic ion and alloy anode
The present invention relates to have battery and other electrochemical structure of the aforesaid anode of forming by reactive metal.Preferred active metal electrode is made up of lithium (Li).The suitable anodes electrolyte that is used for these structures and battery as mentioned above.
The invention still further relates to the electrochemical structure of have active metallic ion (for example lithium-carbon) or active metal alloy (for example Li-Sn) anode.Some structures can have uncharged active metallic ion insert material (for example carbon) at first or be imposed the metal of alloying (for example tin (Sn)) of electric charge subsequently by reactive metal or active metallic ion.Although the present invention mainly describes in conjunction with lithium herein as an example applicable to various reactive metals.
Can use in the conventional Li-ion battery material with carbon element commonly used especially petroleum coke and carbonaceous mesophase spherules carbon as the anode material in the moisture battery cell of Li-ion.Also can use the lithium alloy that comprises one or more metals of being selected among Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and the Sb, preferred Al, Sn or Si anode material as this battery.In a kind of specific embodiment, anode comprises Li, Cu and Sn.
The anolyte of this structure can for example, be dissolved in nonaqueous solvents such as EC, PC, DEC, DMC, EMC, MA, the binary of MF or the LiPF in the ternary mixture commonly used in the conventional Li-ion battery in conjunction with supporting salt 6, LiBF 4, LiAsF 6, LiClO 4, LiSO 3CF 3, LiN (CF 3SO 2) 2Or LiN (SO 2C 2F 5) 2Also can use gel-polymer dielectric, for example comprise that a kind of above-mentioned salt, polymer adhesive such as PVdF, PVdF-HFP copolymer, PAN or PEO and plasticizer (solvent) are as EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1, the electrolyte of 2-DME and composition thereof.
For the battery that uses these anodes, can increase suitable cathode construction to the electrochemical structure on the protection structure opposite side.This structure uses the Li-ionic battery of a large amount of specific cathodes such as air, water, metal hydride or metal oxide to become possibility.For the moisture battery cell of Li-ion, for example, moisture catholyte can be alkalescence, acidity or neutral, and comprises the Li cation.An example of suitable moisture catholyte is 2M LiCl, 1M HCl.
In the initial charge of the battery with lithium-carbon lithium alloy anode, the Li cation is delivered to anode surface by protection structure (comprising anolyte) from catholyte, as in the conventional Li-ion battery telescopiny takes place there.In one embodiment, anode before battery assembling externally by chemistry or electrochemistry lithiumation.
Battery design
Can have any suitable geometry according to electrochemical structure of the present invention and battery cell.For example, consider the description of structure provided herein or battery component, by piling up the acquisition plane geometric shape according to being suitable for the plane layer of cells known Battery pack manufacturing technology of the present invention easily with the various parts (anode, intermediate layer, negative electrode etc.) of structure or battery.These layers that pile up can be designed to prismatic structure or battery.
Perhaps, use tubular glass or glass-ceramic electrolyte to allow to make up the little high surface anode of sealing area with on-waterborne lit-par-lit structure.Opposite with seal length with the slab design that the battery table area increases, the sealing of tubular structure utilization end, sealing area is constant to improve surface area wherein can to increase the length of pipe.This allows to make up should corresponding high surface Li/ water and Li/ air cell with high power density.
The use of on-waterborne lit-par-lit structure of the present invention helps making up.Beginning (sealing is arranged) or closed end glass or glass-ceramic (promptly waterproof substantially active metallic ion conducting solid electrolyte) tube portion is equipped with aforesaid non-water organic bath (anolyte or transfer electrolyte), for example generally is used in the electrolyte in the lithium primary cell.To be inserted in the pipe by the lithium metal bar that the physical membrane of certain type (for example semi-transparent polymer film, as Celgard, Tonin, polypropylene net etc.) surrounds with current-collector.Use simple epoxy sealing, glass to metal seal or other suitable sealing physics to keep apart lithium and environment.
Then protected anode is inserted in the cylindric air electrode and makes cylindrical battery, as shown in Figure 3A.Maybe anode array can be inserted in the prism-shaped air electrode, shown in Fig. 3 B.
By with as this paper suitable moisture, metal hydride recited above or metal oxide cathode system replacement air electrode, also can use this technique construction Li/ water, Li/ metal hydride or Li/ metal oxide battery.
Except using lithium metal bar or silk (in capillary), the present invention also is used to keep apart rechargeable LiC xAnode and moisture or other corrosive atmosphere.In this case, in sheath, use suitable anolyte (transfer electrolyte) solvent on the lithiated carbon electrode, to form passivating film.This will allow to use a large amount of specific cathodes such as air, water, metal hydride or metal oxide to make up high surface Li-ionic battery, for example as shown in Figure 3.
Embodiment
The following examples provide the details of explanation according to the useful performance of Li metal of the present invention and the moisture battery cell of Li-ion.Provide these embodiment to come illustration and be illustrated more clearly in content of the present invention, and never to plan be restrictive.
Embodiment 1:Li/ seawater battery
Carry out a series of tests, the commercial ionic conducting glass-pottery that wherein uses OHARA company is as the film that separates moisture catholyte and non-water anolyte.Battery structure is Li/ nonaqueous electrolyte/glass-ceramic/aqueous electrolyte/Pt.The thickness that uses Chemetall Foote company is that 125 microns lithium paper tinsel is as anode.The thickness of glass-ceramic is in the scope of 0.3-0.48mm.Use two O shape rings that glass-ceramic is fixed in the electrochemical cell, make glass-ceramic be exposed to aqueous environment and be exposed to non-water environment from opposite side from a side.In this case, aqueous electrolyte comprises uses Aquarium Systems, the artificial sea water of " InstantOcean " preparation of the 35ppt of Inc.The conductivity of measuring seawater is 4.5 * 10 -2S/cm.The micropore Celgard barrier film that is placed on the glass-ceramic opposite side is full of by the 1M LiPF that is dissolved in the propylene carbonate 6The nonaqueous electrolyte of forming.The admission space of nonaqueous electrolyte is 0.25ml/1cm 2Lithium electrode surface.When finishing battery circuit, use the platinum counterelectrode that is immersed in fully in the seawater catholyte to promote hydrogen reduction.Use the electromotive force of Li anode in the Ag/AgCl reference electrode control battery.The value of measuring is recalculated into the electromotive force of standard hydrogen electrode (SHE) scale.Observe the most closely corresponding to Li/Li in the water +And H 2/ H +Between the open circuit potential (OCP) of thermokinetics potential difference be 3.05 volts (Fig. 4).When closing of circuit, to observe hydrogen at Pt electrode place immediately and separate out, it is the indication of anode and cathode electrode reaction in the battery, 2Li=2Li ++ 2e -And 2H ++ 2e -=H 2It is 0.3mA/cm that the velocity of discharge is provided among Fig. 2 2The time Li anodic solution electromotive force-time graph.The result is indicated as the working battery with stable discharging voltage.Should emphasize that in the Total Test that uses the Li anode that directly contacts seawater, the non-constant of the utilance of Li is because extremely high Li corrosion rate (surpasses 19A/cm in the seawater 2), can not use this class battery being similar under used those the low and medium current density of this embodiment at all.
Embodiment 2:Li/ air cell
Battery structure is similar to the structure among the embodiment of front, but the Pt electrode is immersed in the electrolyte fully, and this test cell has the air electrode of making for commercial Zn/ air cell.Used aqueous electrolyte is 1M LiOH.Li anode and nonaqueous electrolyte are with identical described in the embodiment of front.
The open circuit potential of observing this battery is 3.2V.Fig. 5 has shown that the velocity of discharge is 0.3mA/cm 2The time discharge voltage time curve.Battery table revealed the discharge voltage of 2.8-2.9V above 14 hours.This result shows that the Li/ air cell with the solid electrolyte film that separates moisture catholyte and non-water anolyte can obtain superperformance.
Embodiment 3:Li-ion battery
In these trials, use the commercial ionic conducting glass-pottery of OHARA company as the film that separates moisture catholyte and non-water anolyte.Battery structure is carbon/nonaqueous electrolyte/glass-ceramic/aqueous electrolyte/Pt.Carbon electrode commonly used in use and the lithium ion battery comprises that similarly the commercial carbon electrode on copper substrate of synthetic graphite is as anode.The thickness of glass-ceramic is 0.3mm.Use two O shape rings that glass-ceramic is fixed in the electrochemical cell, make glass-ceramic be exposed to aqueous environment and be exposed to non-water environment from opposite side from a side.Aqueous electrolyte comprises 2M LiCl and 1M HCl.The two-layer micropore Celgard barrier film that is placed on the glass-ceramic opposite side is full of nonaqueous electrolyte, and nonaqueous electrolyte comprises the 1M LiPF in the mixture that is dissolved in ethylene carbonate and dimethyl carbonate (volume ratio 1: 1) 6Between two-layer Celgard barrier film, place lithium line reference electrode so that the electromotive force of carbon anode in the Control Circulation process.Use the platinum guaze that is immersed in fully in 2M LiCl, the 1M HCl solution as cell cathode.Use is placed on the electromotive force of the Ag/AgCl reference electrode control carbon electrode in the aqueous electrolyte and strides across the voltage drop of glass-ceramic, and the electromotive force of Pt negative electrode in the cyclic process.The open circuit voltage (OCV) of observing this battery is about 1 volt.Observe and tight corresponding Li reference electrode of thermokinetics value and Ag/AgCl reference electrode between voltage difference be 3.2 volts.With 0.1mA/cm 2For battery charge reaches 5mV up to carbon electrode to Li reference electrode electromotive force, use identical cut-off potential then with 0.05mA/cm 2Charging.The velocity of discharge is 0.1mA/cm 2, carbon anode is 1.8V to the discharge cut-off potential of Li reference electrode.Data among Fig. 6 show to have the embedding carbon anode and can reversibly work with the battery that contains the cationic aqueous electrolyte of Li.This is to use the aqueous solution to replace solid lithiumation oxide coated cathode to be used for first known example of carbon anode charging as the Li ion source in the Li ion battery.
Embodiment 4: the performance of thick Li anode in aqueous electrolyte of glass-ceramic protection
Design test is used for the test Li/ water battery at the various Li paper tinsel of aqueous electrolyte thickness.Battery shown in Figure 8 comprises and has that active area is 2.0cm on the Cu substrate 2The anode chamber of protected Li paper tinsel anode.Thickness is made by the Li metal bar for the Li electrode of about 3.3-3.5mm.Manufacture process comprises to be extruded and rolling Li rod, and the paper tinsel that utilizes hydraulic press static state to be expressed to then to obtain is to the surface of Ni net current-collector.The mould that use has a polypropylene bodies is used for extrusion operation to avoid the chemical reaction with the Li paper tinsel.Use two O shapes ring with thickness for about 50 microns glass-ceramic film is fixed in the electrochemical cell, make the glass-ceramic film be exposed to aqueous environment (catholyte) and be exposed to non-water environment (anolyte) from opposite side from a side.Anolyte provides the liquid intermediate layer between anode and glass-ceramic film surface.
Battery is full of 4M NH 4The moisture catholyte of Cl, this allows negative electrode to be cushioned in battery storage and discharge process.The micropore Celgard barrier film that is placed on the glass-ceramic film opposite side is full of by the 1M LiClO that is dissolved in the propylene carbonate 4The non-water anolyte of forming.The anode chamber is sealed facing to the aqueous solution, thereby has only cover glass-ceramic membrane to be exposed to aqueous environment, reference electrode and wire netting counterelectrode.The cell body of being made by borosilicate glass is full of the 100ml catholyte.Use Ti net counterelectrode to separate out (water reduction) to promote the hydrogen in the Li anodic dissolution processes as negative electrode.The Ag/AgCl reference electrode that uses next-door neighbour's cover glass film surface to place is controlled the electromotive force of Li anode in the discharge process.The value of measuring is recalculated into the electromotive force of standard hydrogen electrode (SHE) scale.Battery has the steam vent of the hydrogen that discharges the generation of negative electrode place.
Electromotive force-the time graph that has shown the continuous discharge of this battery among Fig. 7.Battery shows almost 1400 hours very long discharge under the closed circuit voltage of about 2.7-2.9V.The discharge capacity value that obtains is very big, about 650mAh/cm 2Remove Li along Li anode/aqueous electrolyte interface, do not destroy the thick cover glass-ceramic membrane of 50 μ m above 3.35mm.The thickness of the Li paper tinsel that uses in this experiment is in the scope of 3.35-3.40mm.The ex-post analysis of the Li anode of discharge confirms that all the Li of amount peels off from the Ni current-collector when battery discharge finishes.This coulombic efficiency that proves protected Li anode discharge is near 100%.
Use the Li discharge capacity that obtains to infer the performance of the prismatic battery of Li/ air.In Fig. 9, the specific energy that has shown the battery of the protection Li thickness with variation is inferred and Li thickness is the value of battery weight specific energy of the glass protection anode of 3.3mm.This figure also illustrates battery structure and has shown the parameter of calculating usefulness.Battery size is corresponding to area (about 45cm of business card 2) and the thickness (the Li anode that comprises 3.3mm) of about 6mm.This produces the predictive ability of very large 90Wh.Can be as can be seen from Figure 9, the discharge capacity of glass-protection anode that test obtains allows the Li/ air cell of build exception high performance nature.
Another embodiment-Li/ water battery and the hydrogen generator that is used for fuel cell
Use allows to make up the above-mentioned reactive metal/water battery that can ignore corrosion current that has according to the structure of the protection on the active metal electrode of the present invention.The Li/ water battery has the very high theoretical energy density of 8450Wh/kg.Cell reaction is Li+H 2O=LiOH+1/2H 2Although hydrogen that cell reaction produces generally is usefulness no longer, in this embodiment of the present invention, be used to the ambient temperature fuel cell that fuel is provided.The hydrogen that produces can be delivered directly to fuel cell or can be used for recharging to be used in the fuel cell after a while for metal hydride alloy.At least one Millenium Cell of company " Http:// www.millenniumcell.com/news/tech.html" utilize the reaction of sodium borohydride and water to produce hydrogen.But this reaction needed is used catalyst, and by NaBH 4Lose as heat with the energy that the chemical reaction of water produces.
NaBH 4+2H 2O→4H 2+NaBO 2
When with fuel cell reaction H 2+ O 2=H 2O in conjunction with the time, fuel cell reaction is considered to:
NaBH 4+2O 2→2H 2O+NaBO 2
Can be by NaBH 4The equivalent of reactant calculates the energy density (38/4=9.5 gram/equivalent) of this system.NaBH 4The gravimetric analysis capacity be 2820mAh/g; Because cell voltage is about 1, so the specific energy of this system is 2820Wh/kg.If based on end product NaBO 2Calculating energy density, then energy density is lower, about 1620Wh/kg.
Under the situation of Li/ water battery, hydrogen produces by being considered to and is undertaken by electrochemical reaction described below:
Li+H 2O＝LiOH+1/2H 2
In this case, the energy of chemical reaction is converted to 3 volts of electric energy in the battery, in fuel cell hydrogen is changed into water then, and overall reaction is considered to by following described:
Li+1/2H 2O+1/4O 2＝LiOH
Wherein all chemical energy in theory all is converted to electric energy.Under about 3 volts cell voltage potential, be 3830mAh/g based on the energy density of lithium anode, for 11500Wh/kg (compares NaBH 4High 4 times).If comprise the weight of the water of reaction needed, then energy density is 5030Wh/kg.If energy density is based on the weight of discharging product LiOH, then it is 3500Wh/kg, or is NaBO 2The twice of maximum system energy density.This can compare with previous notion, has considered the reaction of lithium metal and water generates hydrogen in the previous notion equally.Under the sort of situation, energy density is lowered 3 times, because Li/H 2Most of energy in the O reaction is depleted as heat, and energy density is based in fact less than 1 H 2/ O 2Right cell voltage potential is (with Li/H 2O's is 3 opposite).In of the present invention this embodiment shown in Figure 10, also can control the generation of hydrogen carefully by the load on the Li/ water battery, the pot-life that the Li/ water battery is long owing to diaphragm has, and the hydrogen that leaves battery is used for H by humidification 2/ air-fuel battery.
Conclusion
Although described foregoing invention in greater detail for clear understanding, obviously can implement some changes and improvements within the scope of the invention.Especially, although mainly described the present invention with reference to lithium metal, alloy or embedding anode, anode also can be made up of any reactive metal especially other alkali metal such as sodium.Should note existing the multiple alternative of implementing method of the present invention and composition.Therefore, it is illustrative and not restrictive that embodiment of the present invention are considered to, and the invention is not restricted to the details that this paper provides.
Whole documents that this paper quotes are incorporated herein by reference for various purposes.

Claims (82)

1. Electrochemcial cell structures comprises:
Anode, this anode comprise the material that is selected from reactive metal, active metallic ion, active metal alloy metal and the reactive metal insert material; With
Ionic conduction protection structure on the anode first surface, this structure comprises:
Comprise active metallic ion conductive diaphragm layer with the semipermeable membrane of the non-water anolyte dipping of liquid phase or gel phase, this membrane layer and reactive metal chemical compatible and contact anode and
Compatible with membrane layer and aqueous environment chemistry and contact the waterproof substantially ion conductive layer of membrane layer, wherein said waterproof substantially ion conductive layer contains the material that is selected from glassy state or amorphous state active metallic ion conductor, ceramic active metallic ion conductor and the glass-ceramic active metallic ion conductor.
2. the structure of claim 1, wherein pellicle is a microporous polymer.
3. the structure of claim 2, wherein anolyte is in liquid phase.
4. the structure of claim 3, wherein anolyte comprises the solvent that is selected from organic carbonate, ether, ester, formic acid esters, lactone, sulfone, sulfolane and the combination thereof.
5. the structure of claim 4, wherein anolyte comprises solvent and supports salt, wherein solvent is selected from EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1, and 2-DME or senior glyme, sulfolane, methyl formate, methyl acetate and their combination are supported salt and be selected from LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiSO 3CF 3, LiN (CF 3SO 2) 2And LiN (SO 2C 2F 5) 2
6. the structure of claim 5, wherein anolyte also comprises 1, the 3-dioxolanes.
7. the structure of claim 2, wherein anolyte is in gel phase.
8. the structure of claim 7, wherein anolyte comprises gelling agent, plasticizer and Li salt, gelling agent is selected from PVdF, PVdF-HFP copolymer, PAN and PEO and their mixture; Plasticizer is selected from EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME and their mixture; Li salt is selected from LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiSO 3CF 3, LiN (CF 3SO 2) 2And LiN (SO 2C 2F 5) 2
9. the structure of claim 1, wherein said reactive metal is an alkali metal.
10. the structure of claim 1, wherein reactive metal is lithium or lithium alloy.
11. the structure of claim 10, wherein waterproof substantially ion conductive layer is for having following composition and comprising by Li 1+x(M, Al, Ga) x(Ge 1-yTi y) 2-x(PO 4) 3And/or Li 1+x+yQ xTi 2-xSi yP 3-yO 12Ionic conducting glass-the pottery of the principal crystalline phase of forming:
Form:
P 2O 5 26-55mol％
SiO 2 0-15mol％
GeO 2+TiO 2 25-50mol％
GeO wherein 20-50mol%
TiO 2 0-50mol％
ZrO 2 0-10mol％
M 2O 3 0＜10mol％
Al 2O 3 0-15mol％
Ga 2O 3 0-15mol％
Li 2O 3-25mol％
Li wherein 1+x(M, Al, Ga) x(Ge 1-yTi y) 2-x(PO 4) 3Middle X≤0.8 and 0≤Y≤1.0, M is the element that is selected from Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, Li 1+x+yQ xTi 2-xSi yP 3-yO 12In 0＜X≤0.4 and 0＜Y≤0.6, Q is Al or Ga.
12. the structure of claim 1, wherein waterproof substantially ion conductive layer has at least 10 -5The ionic conductivity of S/cm.
13. the structure of claim 1, wherein the nonaqueous electrolyte membrane layer has at least 10 -5The ionic conductivity of S/cm.
14. the structure of claim 1, wherein anode comprises reactive metal.
15. the structure of claim 1, wherein anode comprises active metallic ion.
16. the structure of claim 1, wherein anode comprises the active metal alloy metal.
17. the structure of claim 16, wherein the active metal alloy metal is selected from Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb.
18. the structure of claim 1, wherein anode comprises the reactive metal insert material.
19. the structure of claim 18, wherein the reactive metal insert material comprises carbon.
20. a battery cell comprises:
Electrochemcial cell structures according to aforementioned any claim; With
Cathode construction.
21. the battery of claim 20, wherein cathode construction comprises electron conduction parts, ionic conduction parts and electro-chemical activity parts, and wherein at least a cathode construction parts comprise aqueous ingredients.
22. the battery of claim 21, wherein cathode construction comprises moisture electro-chemical activity parts.
23. the battery of claim 22, wherein moisture electro-chemical activity parts are water.
24. the battery of claim 23, wherein moisture electro-chemical activity parts comprise the water-soluble oxidizers that is selected from gaseous state, liquid state and solid oxide agent and combination thereof.
25. the battery of claim 24, wherein water-soluble gaseous oxidizer is selected from O 2, SO 2And NO 2, water-soluble solid oxide agent is selected from NaNO 2, KNO 2, Na 2SO 3And K 2SO 3
26. the battery of claim 24, wherein water-soluble oxidizers is a peroxide.
27. the battery of claim 26, wherein water-soluble oxidizers is a hydrogen peroxide.
28. the battery of claim 21, wherein ionic conduction parts and electro-chemical activity parts are made of aqueous electrolyte.
29. the battery of claim 28, wherein aqueous electrolyte is selected from strong acid solution, weak acid solution, alkaline solution, neutral solution, both sexes solution, peroxide solutions and their combination.
30. the battery of claim 28, wherein aqueous electrolyte comprises and is selected from HCl, H 2SO 4, H 3PO 4, acetate/lithium acetate, LiOH, seawater, LiCl, LiBr, LiI, NH 4Cl, NH 4Member in the aqueous solution of Br and hydrogen peroxide and the combination thereof.
31. the battery of claim 30, wherein aqueous electrolyte is a seawater.
32. the battery of claim 30, wherein aqueous electrolyte comprises seawater and hydrogen peroxide.
33. the battery of claim 30, wherein aqueous electrolyte comprises acidic peroxide solution.
34. the battery of claim 30, wherein hydroperoxide dissolution is in flowing through the aqueous electrolyte of battery.
35. the battery of claim 21, wherein cathode construction electron conduction parts are the porous catalytic carrier.
36. the battery of claim 35, wherein porous catalytic electron conduction carrier comprises nickel.
37. the battery of claim 35 is wherein handled porous catalytic electron conduction carrier with ionomer.
38. the battery of claim 22, wherein the cathode construction electrochemical active material comprises air.
39. the battery of claim 38, wherein air comprises moisture.
40. the battery of claim 39, wherein ion conductive material comprises aqueous ingredients.
41. the battery of claim 40, wherein ion conductive material also comprises ionomer.
42. the battery of claim 41, wherein ion conductive material comprises neutrality or acid water base electrolyte.
43. the battery of claim 42, wherein aqueous electrolyte comprises LiCl.
44. the battery of claim 42, wherein aqueous electrolyte comprises NH 4A kind of among Cl and the HCl.
45. the battery of claim 21, wherein cathode construction comprises air diffusion membrane, hydrophobic polymer layer, oxygen reduction catalyst, electrolyte and electron conduction parts/current-collector.
46. the battery of claim 45, wherein electron conduction parts/current-collector comprises the nickel porous material.
47. the battery of claim 45 also comprises the barrier film that is arranged between diaphragm and the cathode construction.
48. the battery of claim 21, wherein cathode construction electro-chemical activity parts comprise metal hydride alloy.
49. the battery of claim 48, wherein cathode construction ionic conduction parts comprise aqueous electrolyte.
50. the battery of claim 49, wherein aqueous electrolyte is acid.
51. the battery of claim 50, wherein aqueous electrolyte comprises halide acid or acid salt.
52. the battery of claim 51, wherein aqueous electrolyte comprises chloride or bromide acid or acid salt.
53. the battery of claim 52, wherein aqueous electrolyte comprises HCl, HBr, NH 4Cl and NH 4A kind of among the Br.
54. the battery of claim 53, wherein metal hydride alloy comprises AB 5And AB 2A kind of in the alloy.
55. the battery of claim 20, wherein battery is a primary cell.
56. the battery of claim 20, wherein battery is a rechargeable battery.
57. the battery of claim 20, wherein battery has slabbed construction.
58. the battery of claim 20, wherein battery has tubular structure.
59. the battery of claim 21, wherein reactive metal is a lithium, and cathode construction comprises moisture ionic conduction parts and transition metal oxide electro-chemical activity parts.
60. the battery of claim 59, wherein transition metal oxide is selected from NiOOH, AgO, iron oxide, lead oxide and manganese oxide.
61. the battery of claim 20, wherein anolyte also comprises water insoluble or a small amount of water-soluble polymer monomer, and the catholyte of cathode construction comprises the polymerization initiator of monomer.
62. the battery of claim 61, wherein monomer is 1, the 3-dioxolanes.
63. the battery of claim 62, wherein polymerization initiator comprises at least a in the Bronsted acid that is dissolved in the catholyte and the water-soluble lewis acid.
64. the battery of claim 63, wherein polymerization initiator comprises benzo benzoyl cation.
65. the battery of claim 20, wherein cathode construction comprises the ionic conduction parts.
66. the battery of claim 65, wherein the ionic conduction parts comprise non-water catholyte.
67. the battery of claim 66, wherein catholyte comprises and is selected from organic liquid and ion liquid material.
68. the battery of claim 67, wherein catholyte is the solution of Li salt in aprotic solvent, and aprotic solvent is selected from organic carbonate, ether, lactone, sulfone, ester, formic acid esters and their combination.
69. the battery of claim 68, wherein catholyte is selected from EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME and senior glyme, 1,3-dioxolanes, sulfolane, methyl formate, methyl acetate and their combination are supported salt and are selected from LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiSO 3CF 3, LiN (CF 3SO 2) 2, LiN (SO 2C 2F 5) 2With their combination.
70. the battery of claim 69, what also comprise dissolving is selected from lithium polysulfide, NO 2, SO 2, SOCl 2Solid-state, liquid state or gaseous oxidizer.
71. the battery of claim 66, wherein catholyte comprises the ionic liquid that is selected from imdazole derivatives, pyridine derivate, phosphine compound and tetraalkyl ammonium compound and the combination thereof.
72. the battery of claim 71, wherein ionic liquid is selected from 1-ethyl-3-methylimidazole toluene fulfonate (EMIM-Ts), 1-butyl-3-methylimidazole octyl sulfate (BMIM-OctSO4), 1-ethyl-3-methylimidazole hexafluorophosphate and 1-hexyl-3-methyl imidazolium tetrafluoroborate.
73. the battery of claim 20, wherein this battery has greater than 10mAh/cm 2Discharge capacity.
74. the battery of claim 73, wherein this battery has greater than 100mAh/cm 2Discharge capacity.
75. the battery of claim 74, wherein this battery has greater than 500mAh/cm 2Discharge capacity.
76. the battery of claim 30, wherein anode is the thick Li of 3.35mm, and this battery is full of and comprises NH 4The aqueous electrolyte of Cl, and this battery has 650mAh/cm 2Discharge capacity.
77. the battery of claim 38, wherein this battery has 3.3mm thick Li anode and 45cm 2Area, Feng Zhuan specific energy is not 3400Wh/l.
78. the battery of claim 77, wherein this battery has 70% encapsulation load, and the specific energy of encapsulation is 1000Wh/l.
79. the battery of claim 23 also comprises the PEMH that catches the hydrogen that cathode construction discharges in the battery cell redox reaction 2/ O 2Fuel cell.
80. a manufacturing comprises according to the method for the battery cell of claim 20:
Provide with lower member:
Active metal anodes;
Cathode construction; With
Ionic conduction protection structure on the anode first surface, this structure comprises:
The active metallic ion conductive diaphragm layer that comprises non-water anolyte, this membrane layer and reactive metal chemistry compatible and contact anode and
Compatible with membrane layer and cathode construction chemistry and contact the waterproof substantially ion conductive layer of cathode construction; With
Assemble above-mentioned parts.
81. the method for claim 80, wherein waterproof substantially ion conductive layer are tubulose.
82. a method that is used for stopping under the situation of structural failure according to the electrochemical cell of claim 20, being included in provides water insoluble or a small amount of water-soluble polymer monomer in the anolyte, the polymerization initiator of monomer is provided in catholyte.
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