CN100438195C - A Li-ion secondary battery - Google Patents

A Li-ion secondary battery Download PDF

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Publication number
CN100438195C
CN100438195C CNB2004100273518A CN200410027351A CN100438195C CN 100438195 C CN100438195 C CN 100438195C CN B2004100273518 A CNB2004100273518 A CN B2004100273518A CN 200410027351 A CN200410027351 A CN 200410027351A CN 100438195 C CN100438195 C CN 100438195C
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lithium
stratiform
spinel structure
lithium manganate
manganate
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CN1700498A (en
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姜占峰
董俊卿
王传福
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BYD Co Ltd
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BYD Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a lithium ion secondary battery which comprises a positive pole, a negative pole, an electrolyte and a membrane, wherein an active material of the positive pole is formed by mixing spinel type lithium manganate and laminar nickel acid lithium according to a proportion of 1 to 9: 9 to 1 (part by weight), and the ratio of average particle diameters of the spinel type lithium manganate to the laminar nickel acid lithium is 1.5 to 8. The spinel type lithium manganate and the laminar nickel acid lithium are mixed and used by the present invention, the mixing ratio and the average particle diameters of the two kinds of substances are controlled, and thus, the orientating control of the spinel type lithium manganate to the laminar nickel acid lithium and the control of the laminar nickel acid lithium to the Jahn-Teller effect of the spinel type lithium manganate are realized. Therefore, a nonaqueous lighium secondary cell which has the advantages of low cost, high capacity, good heat stability, good high-current discharge performance and little attenuation under high temperatures is obtained.

Description

A kind of lithium rechargeable battery
Technical field
The present invention relates to the battery that electric equipment products are used, particularly relate to a kind of lithium rechargeable battery.
Background technology
Along with developing rapidly of electronics industry, information industry, people are more and more higher to the requirement of all kinds of electric product power supplys, and wherein lithium rechargeable battery is widely used with its many superior function.The positive electrode that lithium battery uses mainly is an intercalation compounds, the at present operable stratiform cobalt acid lithium (LiCoO that mainly contains 2), stratiform lithium nickelate (LiNiO 2) and lithium manganate having spinel structure (LiMn 2O 4).The positive electrode of extensive use is stratiform cobalt acid lithium LiCoO 2Material.
Stratiform cobalt acid lithium and stratiform lithium nickelate and various derivative products (by the doping of zwitterion or the modes such as coating of other materials) thereof are though have higher specific discharge capacity, but their thermal stabilitys under charged state are relatively poor, and cobalt and nickel as raw material cost an arm and a leg, and have the problem of shortage of resources.
Though its raw material manganese resource content of lithium manganate having spinel structure is abundant, low price, and the thermal stability height under the charged state, thus the advantages such as security performance of battery improved, but it exists specific discharge capacity low, serious problems such as capacity attenuation is violent under the high temperature have limited its industrial applications.
For this reason, in Japanese patent laid-open 9-293538 and Chinese patent CN1262532A, propose to attempt improving the partial properties of lithium manganate having spinel structure by interpolation stratiform cobalt acid lithium and lithium nickelate in lithium manganate having spinel structure.But disclosed method and insufficient in the above-mentioned patent, mainly be when improving battery high-temperature shelf characteric and security performance, reduced the capacity of battery, perhaps improved technology difficulty that battery is made (requirement is done pole piece thin) or the like, and do not had fully to excavate the improvement effect of lithium manganate having spinel structure stratiform cobalt acid lithium and stratiform lithium nickelate.In addition, because stratiform lithium nickelate discharge platform (3.7V) is lower than stratiform cobalt acid lithium (3.8V), makes the stratiform lithium nickelate be better than stratiform cobalt acid lithium, so do not use stratiform cobalt acid lithium among the present invention the over effect of lithium manganate having spinel structure.
Also because the unit cell volume contraction when charging of lithium manganate having spinel structure material, and volumetric expansion when discharge, and overdischarge takes place in positive plate surface portion zone easily when discharge, the Jahn-Teller effect takes place, generate the relatively poor cubic system of chemical property, and this variation is at high temperature especially violent, becomes to cause the violent main cause of capacity attenuation under the lithium manganate having spinel structure high temperature.And on the other hand, stratiform cobalt acid lithium structure cell when charging expands, structure cell shrinks when discharge, and because cobalt acid lithium is a layer structure, the orientation height is easy to take place parallel-oriented with respect to collector body, thereby the impregnability based on electrolyte reduces, with than heavy-current discharge the time, transportable lithium ion quantity reduces, and causes the reduction of capacity.
Summary of the invention
The present invention is intended to effectively overcome lithium manganate having spinel structure and stratiform cobalt acid lithium and the stratiform lithium nickelate limitation separately as the positive source material, and provide a kind of excellent combination property, with low cost, the capacity height, Heat stability is good, good heavy current, the little lithium rechargeable battery of capacity attenuation under the high temperature.
For achieving the above object, the invention provides a kind of lithium rechargeable battery, this battery comprises positive pole, negative pole, electrolyte and barrier film, it is characterized in that, the active material of described positive pole is mixed by lithium manganate having spinel structure and stratiform lithium nickelate, its main purpose is, the two can produce on the change in volume complementary when discharging and recharging, thereby dissociating between the reduction active material particle, keep outside the higher current collecting efficiency, the stratiform lithium nickelate can effectively suppress overdischarge on the LiMn2O4 particle (because stratiform lithium nickelate electron conductivity is than lithium manganate having spinel structure height, therefore overdischarge at first occurs on the stratiform lithium nickelate particle), thus the generation of the Jahn-Teller effect of inhibition lithium manganate having spinel structure; Lithium manganate having spinel structure can play inhibitory action to the orientation trend of stratiform lithium nickelate.
In order to realize effect above-mentioned, with lithium manganate having spinel structure and the stratiform lithium nickelate mixed by 1～9: 9～1 (weight portions), its preferred mixed proportion is 3～7: 7～3.
In use, because the lithium manganate having spinel structure specific discharge capacity is lower, and tap density is slightly little, thereby causes lithium manganate having spinel structure system specific capacity very low.In order to satisfy the capacity requirement of battery, when using mixed cathode active material, must increase the anode dressing amount, thereby need higher anode dressing density, need bigger pressure to come compressing tablet during the positive plate film-making.If the lithium manganate having spinel structure average grain diameter is less than stratiform lithium nickelate average grain diameter, just can't the orientation trend of stratiform lithium nickelate under the high pressure be suppressed, the stratiform lithium nickelate takes place parallel-oriented with respect to collector body, the channel parallel of lithium ion migration is in collector body, and the electrolyte impregnability is not high, cause the difficulty of lithium ion migration, this problem is especially outstanding when heavy-current discharge.
If the average grain diameter of lithium manganate having spinel structure is greater than the average grain diameter of stratiform lithium nickelate.Lithium manganate having spinel structure can suppress the orientation of stratiform lithium nickelate, and promptly when applying big pressure, the pressure between lithium manganate having spinel structure and the stratiform lithium nickelate will suitably be disperseed.
It is 1.5～8 that the present invention requires the lithium manganate having spinel structure and the average grain diameter ratio of stratiform lithium nickelate, and its preferred average grain diameter ratio is 2～6.
Satisfying under the prerequisite of above-mentioned size ratio; if the average grain diameter of lithium manganate having spinel structure is too little; then the particle of stratiform lithium nickelate can be littler; in order to obtain the positive plate of satisfactory dressing density; need to use bigger pressure; thereby the orientation of stratiform lithium nickelate increases, and can cause the infiltration difficulty of electrolyte.If the average grain diameter of lithium manganate having spinel structure is excessive, the particle of stratiform lithium nickelate also needs corresponding increase, will cause the specific area of material to reduce, and reduces with the contact area of electrolyte, is unfavorable for battery performance.Therefore require that particle is generally between 5～40 μ m in the positive electrode of the present invention in the known particle size range of general positive electrode.
The structural formula of the lithium manganate having spinel structure of mentioning among the present invention is Li 1+xMn 2-yM yO 4, wherein, M is at least a among element M g, Ca, Sr, Ba, Ti, Cr, Fe, Co, Ni, Cu, the Al, and the X value is-0.15～0.15, and the y value is 0～0.5.This shows that the structure of lithium manganate having spinel structure is not limited to LiMn 2O 4Structure, the material that the said structure formula is contained all can use, thereby improves the chemical property in a certain respect (for example specific discharge capacity, normal temperature, high temperature cyclic performance, storge quality, security performance or the like) of this positive electrode.
The structural formula of the stratiform lithium nickelate of mentioning among the present invention is LiNi 1-xM xO 4, wherein, M is at least a among element M g, Ca, Sr, Ba, Ti, Cr, Mn, Fe, Co, Cu, the Al, the X value is 0～0.5.This shows that equally the structure of stratiform lithium nickelate is not limited to LiNiO 2Structure, the material that the said structure formula is contained all can use, thereby improves the chemical property in a certain respect (for example specific discharge capacity, normal temperature, high temperature cyclic performance, storge quality, security performance or the like) of this positive electrode.The preferred LiNi that uses among the present invention 0.8Co 0.2O 2Material.
The active material of positive pole of the present invention is to be mixed by lithium manganate having spinel structure and stratiform lithium nickelate, and add adhesive, conductive agent and solvent after mix, apply, oven dry, compressing tablet make.
Adhesive be fluorine resin and and polyethylene, polyvinyl alcohol; Conductive agent is carbon black, graphite-like material with carbon element; Solvent is N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol.
Contribution of the present invention is that it has effectively overcome lithium manganate having spinel structure and stratiform cobalt acid lithium and the stratiform lithium nickelate limitation separately as the positive source material.After the stratiform lithium nickelate mixing of contraction is used when expanding discharge when the lithium manganate having spinel structure of expansion is with charging when shrinking discharge during with charging, complementary except can when discharging and recharging, producing on the change in volume, thereby dissociating between the reduction active material particle, keep outside the higher current collecting efficiency, the stratiform lithium nickelate can effectively suppress overdischarge on the LiMn2O4 particle (because stratiform lithium nickelate electron conductivity is than lithium manganate having spinel structure height, therefore overdischarge at first occurs on the stratiform lithium nickelate particle), thus the generation of the Jahn-Teller effect of inhibition lithium manganate having spinel structure; Lithium manganate having spinel structure can play inhibitory action to the orientation trend of stratiform lithium nickelate.So just can obtain with low cost, capacity is high, the little non-water anode material of lithium battery of capacity attenuation under the Heat stability is good, good heavy current, high temperature.
Embodiment
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Lithium rechargeable battery of the present invention comprises positive pole, negative pole, electrolyte and barrier film, and wherein said negative pole is coated on the collector body by negative active core-shell material and corresponding adhesive, dispersant, solvent and oven dry, compressing tablet make.Described negative active core-shell material can use lithium metal, the lithium alloy material of doped lithium ion etc. that maybe can mix/go.As the material of the doped lithium ion that can mix/go, example is a carbonaceous material, as the product of roasting of native graphite, Delanium, coke, carbon black, RESEARCH OF PYROCARBON, carbon fiber and organic polymer; And chalcogenide, as the oxide and the sulfide of the doped lithium ion that mixes/go under can be in the lower current potential than positive pole.As carbonaceous material, mainly the carbonaceous material of being made up of graphite material (as native graphite and Delanium) is suitable.Described adhesive can be fluorine resins such as polytetrafluoroethylene, Kynoar and polyethylene, polyvinyl alcohol; Dispersant can be a cellulose; Solvent can be N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol, deionized water.As the collector body that is used for negative pole, can be Copper Foil, stainless steel foil, nickel foil, shape can be mesh-like, paper tinsel shape.Described electrolyte is non-aqueous electrolyte.To electrolyte wherein, the electrolytic salt that can use common nonaqueous electrolytic solution to use, for example LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiSbF 6, LiCl, LiBr, LiCF 2SO 3Deng lithium salts, consider from the oxidation stability angle, preferably select LiClO for use 4, LiPF 6, LiBF 4, LiAsF 6Solvent for use is an organic solvent, can be vinyl carbonate, propylene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, 1,1-or 1,2-dimethoxy ethane, 1, one or more in 2-diethoxy ethane, oxolane, 2-methyltetrahydrofuran, methyl phenyl ethers anisole, ether, N-methyl pyrrolidone, dimethyl formamide, acetonitrile, propionitrile, chlorine nitrile, the ethyl acetate.Described barrier film can be nonwoven fabrics, synthetic resin microporous barrier, preferentially uses the synthetic resin microporous barrier, is excellent with polyolefin microporous film again wherein, and polyethene microporous membrane, microporous polypropylene membrane, polyethylene polypropylene composite micro porous film are specifically arranged.
Main points of the present invention are, the active material of described positive pole by lithium manganate having spinel structure and stratiform lithium nickelate by 1～9: the mixed of 9～1 (weight portions) forms, and the average grain diameter ratio of lithium manganate having spinel structure and stratiform lithium nickelate is 1.5～8.
Prepare lithium rechargeable battery of the present invention, described positive pole is that the lithium manganate having spinel structure that will prepare according to known method and stratiform lithium nickelate mix according to the above ratio and add adhesive, conductive agent and solvent, mixes, applies, oven dry, compressing tablet make.Wherein mixing speed is controlled to be 300～6000rpm, and mixing time is controlled to be 0.2～10 hour.Described adhesive can be fluorine resins such as polytetrafluoroethylene, Kynoar and polyethylene, polyvinyl alcohol; Conductive agent can be carbon black, graphite-like material with carbon element; Solvent can be N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol etc.
The following example can more help to illustrate the present invention.
Embodiment 1
At first preparing structural formula with known method is LiMn 2O 4Lithium manganate having spinel structure and the structural formula of the Co of doping be LiNi 0.8Co 0.2O 2The stratiform lithium nickelate, the stratiform lithium nickelate all refers to this kind material described in following examples and the Comparative Examples.The average grain diameter of control lithium manganate having spinel structure is 20 μ m, and stratiform lithium nickelate average grain diameter is 4 μ m, and the two particle diameter ratio is 5.
The lithium manganate having spinel structure of getting 8 parts (weight) mixes as positive electrode active materials mutually with the stratiform lithium nickelate of 1 part (weight).Adopting the polyvinylidene fluoride PVDF of 2% (weight) is adhesive, the acetylene black of 3% (weight) is conductive agent, the N-N-methyl-2-2-pyrrolidone N-NMP of surplus is a solvent, under the speed of 300～6000rpm, stirred 0.2～10 hour, make it to mix, apply then, oven dry, compressing tablet, wherein mix, apply, dry three processes and all need under vacuum environment, carry out, compressing tablet makes battery anode slice after being cut into specified size.
With the solvent N-N-methyl-2-2-pyrrolidone N-NMP of the adhesive polyvinylidene fluoride PVDF of the native graphite, 5% (weight) of 95% (weight) and surplus mix, apply, oven dry, compressing tablet, make battery cathode sheet after being cut into specified size.In addition, as the active material of negative plate, except using native graphite, can also use other material known, for example carbon black, coke, glass charcoal, charcoal fiber etc. or its mixture, perhaps lithium, lithium alloy etc.
Adopt above-mentioned positive plate, negative plate, electrolyte are lithium hexafluoro phosphate LiPF 6, solvent is the mixed organic solvents of vinyl carbonate, ethylene carbonate, diethyl carbonate, and concentration is 1 mol, and diaphragm paper is polyethylene, polypropylene composite diaphragm paper, promptly makes lithium rechargeable battery of the present invention by common process.
With the lithium rechargeable battery that above-mentioned positive pole and negative pole, electrolyte and barrier film are assembled into, have with low cost, capacity is high, advantages such as capacity attenuation is little under the Heat stability is good, good heavy current, high temperature.
Embodiment 2～embodiment 7 has provided the example of lithium manganate having spinel structure with the different mixed proportion of stratiform lithium nickelate, and its technical indicator test structure really sees Table 1.
Embodiment 2
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 7: 3 in this example, and other process is with embodiment 1.
Embodiment 3
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 5: 5 in this example, and other process is with embodiment 1.
Embodiment 4
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 3: 7 in this example, and other process is with embodiment 1.
Embodiment 5
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 1: 8 in this example, and other process is with embodiment 1.
Comparative Examples 1～4 has provided the experiment comparing result that positive electrode is respectively lithium manganate having spinel structure and stratiform lithium nickelate, and it the results are shown in Table 1.
Comparative Examples 1
Positive electrode uses lithium manganate having spinel structure in this example, and other process is with embodiment 1.
Comparative Examples 2
Positive electrode uses the stratiform lithium nickelate in this example, and other process is with embodiment 1.
Comparative Examples 3
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 15: 1 in this example, and other process is with embodiment 1.
Comparative Examples 4
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 1: 15 in this example, and other process is with embodiment 1.
The battery behavior test
Battery to embodiment and comparative example carries out performance test, and is as follows:
Specific discharge capacity: after the battery charge, be discharged to discharge capacity/positive electrode active materials quality of 3.0V with the electric current of 0.5C first from 4.2V, unit is mAh/g;
Circulation: be called once circulation at the current discharge with 1C to 3.0V with the 1C current charges then to 4.2V, the discharge capacity of acquisition is the capacity of this circulation, and unit is mAh;
High temperature circulation: under 60 ℃, be called once circulation at the current discharge with 1C to 3.0V with the 1C current charges then to 4.2V, the discharge capacity of acquisition is the capacity of this circulation, and unit is mAh;
100 circulation volume conservation rates: (the 100th circulation specific discharge capacity/specific discharge capacity first circulates) * 100%, unit is %;
100 high temperature circulation capability retentions (the 100th high temperature circulation specific discharge capacity/high temperature circulation specific discharge capacity) first * 100%, unit is %;
High-rate performance: with 1C, 3C electric current battery is discharged respectively, relatively the size of its discharge capacity is labeled as 3C/1C, and unit is %;
Thermal stability: the battery that will charge to 4.2V is dissected, and takes out positive plate, after the drying positive pole material is taken off, and carries out the thermogravimetric experiment under air atmosphere, obtains the decomposition temperature of this material, and unit is ℃.
Test result sees Table 1.
Table 1
Sequence number Lithium manganate having spinel structure and stratiform lithium nickelate mixed proportion (weight portion) Specific discharge capacity/mAh/g 100 circulation volume conservation rate/% 100 high temperature circulation capability retention/% Heavy-current discharge performance (3C/1C)/% Thermal stability/℃
Embodiment 1 8∶1 128 90 77 79 270
Embodiment 2 7∶3 135 91 82 78 252
Embodiment 3 5∶5 140 91 88 78 228
Embodiment 4 3∶7 149 91 87 77 215
Embodiment 5 1∶8 165 91 88 75 207
Comparative Examples 1 1 124 89 55 73 293
Comparative Examples 2 0 180 93 72 52 178
Comparative Examples 3 15∶1 125 89 56 73 281
Comparative Examples 4 1∶15 171 92 74 66 193
As can be seen from Table 1, lithium manganate having spinel structure and stratiform lithium nickelate are pressed lithium nickelate mass ratio X between 0.10～0.90 among the present invention, in the time of between being preferably 0.3～0.70, battery has superior comprehensive electrochemical properties, and its specific discharge capacity improves a lot with respect to spinelle manganic acid lithium material; (60 ℃) capacity attenuation is less under the high temperature; And good heavy current; Positive electrode active materials charging back decomposition temperature improves a lot with respect to lithium nickelate, and security performance is better.
Embodiment 8～15 has provided lithium manganate having spinel structure and stratiform lithium nickelate average grain diameter than (D Mn/ D Ni) experiment.
Embodiment 8
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 40 μ m mix (D Mn/ D Ni=0.5) use as positive active material, other process is with embodiment 1.
Embodiment 9
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 20 μ m mix (D Mn/ D Ni=1) use as positive active material, other process is with embodiment 1.
Embodiment 10
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 13 μ m mix (D Mn/ D Ni=1.54) use as positive active material, other process is with embodiment 1.
Embodiment 11
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 10 μ m mix (D Mn/ D Ni=2) use as positive active material, other process is with embodiment 1.
Embodiment 12
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 5 μ m mix (D Mn/ D Ni=4) use as positive active material, other process is with embodiment 1.
Embodiment 13
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 3.3 μ m mix (D Mn/ D Ni=6) use as positive active material, other process is with embodiment 1.
Embodiment 14
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 2.5 μ m mix (D Mn/ D Ni=8) use as positive active material, other process is with embodiment 1.
Embodiment 15
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 2 μ m mix (D Mn/ D Ni=10) use as positive active material, other process is with embodiment 1.
The battery behavior test, same first.
Test result sees Table 2.
Table 2
Sequence number Average grain diameter compares D Mn/D Ni Specific discharge capacity/mAh/g 100 circulation volume conservation rate/% 100 high temperature circulation capability retention/% Heavy-current discharge performance (3C/1C)/% Thermal stability/℃
Embodiment 8 0.5 135 87 78 56 231
Embodiment 9 1 142 90 82 62 231
Embodiment 10 1.5 141 91 85 73 230
Embodiment 11 2 140 92 88 79 230
Embodiment 12 4 141 91 88 79 229
Embodiment 13 6 139 91 84 75 229
Embodiment 14 8 140 92 85 70 226
Embodiment 15 10 136 89 84 63 220
By data in the table 2 as can be seen, lithium manganate having spinel structure is controlled at 1.5≤D with stratiform lithium nickelate average grain diameter ratio Mn/ D Ni≤ 8, preferably at 2≤D Mn/ D NiIn the time of between≤6, can guarantee the heavy-current discharge performance of positive electrode.

Claims (7)

1, a kind of lithium rechargeable battery, comprise positive pole, negative pole, electrolyte and barrier film, it is characterized in that, the active material of described positive pole by lithium manganate having spinel structure and stratiform lithium nickelate by 1～9: the mixed of 9～1 (weight portions) forms, and the average grain diameter ratio of lithium manganate having spinel structure and stratiform lithium nickelate is 1.5～8.
2, lithium rechargeable battery as claimed in claim 1 is characterized in that, the structural formula of described lithium manganate having spinel structure is Li 1+xMn 2-yM yO 4, wherein, M is at least a among element M g, Ca, Sr, Ba, Ti, Cr, Fe, Co, Ni, Cu, the Al, and the X value is-0.15～0.15, and the y value is 0～0.5.
3, lithium rechargeable battery as claimed in claim 1 is characterized in that, the structural formula of layered lithium nickelate is LiNi 1-xM xO 4, wherein, M is at least a among element M g, Ca, Sr, Ba, Ti, Cr, Mn, Fe, Co, Cu, the Al, the X value is 0～0.5.
4, lithium rechargeable battery as claimed in claim 1 is characterized in that, the mixed proportion of lithium manganate having spinel structure and stratiform lithium nickelate is 3～7: 7～3.
5, lithium rechargeable battery as claimed in claim 1 is characterized in that, lithium manganate having spinel structure is 2～6 with the average grain diameter ratio of stratiform lithium nickelate.
6, lithium rechargeable battery as claimed in claim 1, it is characterized in that, the active material of described positive pole is to be mixed by lithium manganate having spinel structure and stratiform lithium nickelate, and add adhesive, conductive agent and solvent after mix, apply, oven dry, compressing tablet make.
7, lithium rechargeable battery as claimed in claim 6 is characterized in that, described adhesive be fluorine resin and and polyethylene, polyvinyl alcohol; Conductive agent is carbon black, graphite-like material with carbon element; Solvent is N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol.
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