CN100563048C - Battery - Google Patents
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- CN100563048C CN100563048C CN 200510120498 CN200510120498A CN100563048C CN 100563048 C CN100563048 C CN 100563048C CN 200510120498 CN200510120498 CN 200510120498 CN 200510120498 A CN200510120498 A CN 200510120498A CN 100563048 C CN100563048 C CN 100563048C
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- positive electrode
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Abstract
The invention discloses a kind of battery, described battery comprises: positive electrode, and wherein the positive electrode active substance layer is formed on the positive electrode collector of being made by the bullion paper tinsel; Negative electrode is made by lithium metal or lithium metal alloy; And spacer body, wherein, in described positive electrode, described positive electrode active substance layer only is formed on the surface of described positive electrode collector, and crooked described positive electrode makes described positive electrode active substance layer face with each other, and described negative electrode is arranged in the part that described positive electrode active substance layer faces with each other.
Description
Technical field
The present invention relates to have the plane primary cell of outstanding battery behavior and productive rate.
Background technology
At present, button (coin) type lithium battery is as the power supply of clock with such as the memory back-up source of the electronic product of personal computer, copier, video camera, game machine etc.In addition, also expectation is applied to the driving power in automatic vending machine, gas meter, flow meter, intelligent lock system, system for monitoring pressure in tyre, onboard navigation system, electronic labelling system etc. in the widely-used temperature range from high temperature to low temperature.
But, in recent years, a large amount of application has been proposed, wherein use the coin shape battery in necessary load characteristic of equipment side and discharge capacity in order to satisfy, a plurality of coin shape batteries are connected in parallel, and have proposed the desired shape of battery (slim).Because the load characteristic and the discharge capacity of the coin shape battery that wherein response area of electrode is very little can not satisfy demands of applications, so made such using method.
Usually, because need welding to wait battery is arranged in the equipment, its processing step becomes very complicated and has greatly limited the design of equipment.In addition, three or more if the quantity of the battery that is connected in parallel is increased to, so because the variation of the capacity between battery has caused problem.For example, may have such worry, discharge capacity is less than the battery of other batteries, even also can continue discharge and cause over-discharge in normal conditions are finished the state of discharge, or such battery is by another battery charge and cause producing gas and internal short-circuit, thereby abnormally dangerous.
In order to solve such problem, can improve the rectangular battery of battery capacity by utilizing space in the battery thereby used.
Therefore, shown in JP-A-6-187998,, can obtain such battery, wherein increase response area, big electric current can be provided, and can realize the size that approaches by electrode being folded into the Folding screen shape and forming battery.
Fig. 1 is the schematic diagram of demonstration according to the structure of the battery of the embodiment among the JP-A-6-187998.Invention according to JP-A-6-187998; provide screening glass 4 for each positive electrode and negative electrode; the surface of the surface of the substrate 3 of described positive electrode by having insulation property with positive electrode active substance 1a coating or the positive electrode collector that is provided with for the substrate 3 with insulation property forms; the surface of the surface of the substrate 3 of described negative electrode by having insulation property with negative electrode active material 2a coating or the negative electrode collector that is provided with for the substrate 3 with insulation property forms; and they are folding with state shown in Figure 1, form cell apparatus thus.In the battery case that cell apparatus is encapsulated in the external container made by metal material or makes by resin material, form battery thus.
Lithium metal or lithium metal alloy are used for the battery of negative electrode therein, and along with discharge is carried out, lithium is consumed and the negative electrode attenuation.But, as above-mentioned JP-A-6-187998 in disclosed coin shape lithium battery or use the situation of metal-back as the battery of outside, metal-back is difficult to sensing because change and the contact condition between the negative electrodes or the contact condition between the positive electrode of the size of the cell apparatus that the consumption of lithium causes, and the positive electrode shell worsens.Therefore, particularly, when discharge finishes, such problem has taken place, that is, the impedance increase and the load characteristic of battery extremely worsen.
Therefore, even expectation solves above problem and a kind of battery that also has load characteristic and outstanding productive rate when discharge receives is provided, although it is slim.
Summary of the invention
The invention provides a kind of battery, comprising:
Positive electrode, wherein the positive electrode active substance layer is formed on the positive electrode collector of being made by the bullion paper tinsel;
Negative electrode is made by lithium metal or lithium metal alloy; With
Spacer body,
Wherein, the described positive electrode collector of being made by the bullion paper tinsel is formed on described spacer body one side, described positive electrode active substance layer is formed at a side of the described positive electrode collector of being made by the bullion paper tinsel, make described positive electrode active substance layer between positive electrode collector and spacer body, and
Described negative electrode is arranged at the opposite side of described spacer body;
The spacer body bending that will have described positive electrode, negative electrode makes described positive electrode collector face with each other.
In order to solve above problem, according to embodiments of the invention, provide a kind of battery, wherein, crooked wherein positive electrode active substance layer only is formed at the positive electrode on the side of the positive electrode collector of being made by metal forming, makes the positive electrode active substance layer face with each other, and passes through spacer body, between the surface that the positive electrode active substance layer faces with each other, be provided with the negative electrode of making by lithium metal or lithium metal alloy.In this embodiment, for bending the sweep of positive electrode also can provide active material layer non-coated portion.
According to embodiments of the invention, provide a kind of battery, wherein, crooked wherein positive electrode active substance layer only is formed at the positive electrode on the side of the positive electrode collector of being made by metal forming, thereby the positive electrode active substance layer faces with each other, and, between the surface that the positive electrode active substance layer faces with each other, be provided with by lithium metal or the pressurization of lithium metal alloy are attached to the negative electrode that the negative electrode collector forms by spacer body.
Preferably, battery has opening at the part or all of lithium pressurization mating surface that is used for the collector of negative electrode.
According to embodiments of the invention, provide a kind of battery, wherein, crooked wherein positive electrode active substance layer only is formed at the positive electrode on the side of the positive electrode collector of being made by metal forming, thereby the positive electrode active substance layer faces with each other, partly be provided with the non-coated portion of positive electrode active substance layer for positive electricity end, and with the back side of positive electrode terminal adhere to non-coated portion or non-coated portion.One end parts of positive electrode can also partly contact to cover negative electrode with another positive electricity end.
According to embodiments of the invention, by electrode preferably is set, can obtain big electrode area, reduced the internal resistance of battery, and can form battery with high battery behavior.Because only the surface coated with metal forming has active material, thus excellent productive rate obtained, and also can reduce the required cost of investment on facilities and equipment.
According to embodiments of the invention, even because when discharge finishes, also can guarantee conduction, so can prevent the unexpected deterioration of load characteristic and reducing of capacity by the negative electrode collector.
In addition, according to embodiments of the invention, by forming the non-coated portion of active material for the end parts on the collector and electrode terminal being arranged on the back side of non-coated portion, prevented that the active material that causes from coming off when the welding electrode terminal, improve productive rate, and can keep high battery capacity.By with the non-coated portion of active material of collector end part with other end part is overlapping and the permission collector is electrical contact with each other, reduced the internal resistance of battery and can improve battery behavior.
Description of drawings
In conjunction with the accompanying drawings, from following description, other features and advantages of the present invention will be more obvious, and wherein, in whole accompanying drawing, similar Reference numeral is indicated same or analogous part.In the accompanying drawings:
Fig. 1 is the cross-sectional view that is used to illustrate the battery structure of JP-A-6-187998;
Fig. 2 is the schematic diagram that has shown the outward appearance of the battery that forms by enforcement first embodiment;
Fig. 3 has been crooked electrode and has formed the cross-sectional view of the situation of electrode assembly;
Fig. 4 is the schematic diagram of the state that shown electrode crooked;
Fig. 5 has shown the cross-sectional view that is used as the structure of outside laminated film when passing through the battery of enforcement first embodiment formation;
Fig. 6 shows the schematic diagram that comes the state of outer enclosure cell apparatus with laminated film;
Fig. 7 shows by sweep being provided the non-coated portion of active material form the cross-sectional view of the situation of cell apparatus;
Fig. 8 A is to be presented at the schematic diagram that collector is taken place in active material layer with the situation of mountain Zhe method (mountain-folding) mode bending the situation of crackle to 8D;
Fig. 9 is presented at the schematic diagram of collector with the state of the situation sweep of mountain Zhe method mode bending;
Figure 10 is presented at the schematic diagram of collector with the sweep of the situation part of mountain Zhe method mode bending;
Figure 11 is the schematic diagram that is presented at the state of the situation mountain Zhe method sweep that suitable non-coated portion is set;
Figure 12 shows that the width of positive electrode of outmost surface is greater than the cross sectional representation of the state of the width of the positive electrode of inner surface;
Figure 13 is the schematic diagram of the battery structure of the end parts that the shown multilayer electrode outstanding situation that prevents negative electrode with the band bonding thus;
The result's that the situation of Figure 14 closed circuit voltage (CCV) that to be the interdischarge interval that is presented at 10mA under-40 ℃ the environment measure in each battery discharge degree of depth (DOD) obtains curve chart;
Figure 15 A is the schematic diagram that shows the silk screen printing step to 15D;
Figure 16 is the cross-sectional view that shows the structure of the lithium battery that uses positive electrode, provides active material non-coated portion for positive electrode by silk screen printing;
Figure 17 is the cross-sectional view of state midway of discharge that show to use the lithium battery of positive electrode, provides active material non-coated portion for positive electrode by silk screen printing;
Figure 18 is the cross-sectional view of done state of discharge that show to use the lithium battery of positive electrode, provides active material non-coated portion for positive electrode by silk screen printing;
Figure 19 is the schematic diagram that shows the negative electrode collector of implementing second embodiment;
Figure 20 is the schematic diagram that shows the negative electrode collector of implementing second embodiment;
Figure 21 is the cross-sectional view that shows the negative electrode collector of implementing second embodiment;
Figure 22 is the cross-sectional view of done state of discharge that show to implement the lithium battery of second embodiment;
Figure 23 is the schematic diagram that shows the negative electrode that uses among the example 3-1;
Figure 24 is the schematic diagram that shows the negative electrode that uses among the comparative example 3-1;
Figure 25 is the curve chart that shows the measurement result among the embodiment 3;
Figure 26 is the schematic diagram that shows the positive electrode structure of first and second embodiment;
Figure 27 is the cross-sectional view by the battery of implementing the 3rd embodiment formation;
Figure 28 is the schematic diagram that shows the positive electrode of implementing the 3rd embodiment;
Figure 29 is the schematic diagram that shows the battery structure of implementing the 3rd embodiment;
Figure 30 is the schematic diagram that shows by the cell apparatus of implementing the 3rd embodiment formation;
Figure 31 is the schematic diagram that shows the manufacture method of the battery of implementing the 3rd embodiment;
Figure 32 is the schematic diagram that shows the outward appearance of the battery of implementing the 3rd embodiment;
Figure 33 is the cross-sectional view that is presented at the battery structure that forms among the comparative example 5-1.
Embodiment
With reference to accompanying drawing at following description embodiments of the invention.
Fig. 2 has shown the structure of implementing battery 10 of the present invention.The outside of battery 10 is made by laminated film 16, and the negative electrode terminal 15 that will be connected to the positive electrode terminal 14 of positive electrode and be connected to negative electrode draws the adhesive segment of laminated film 16, forms battery 10 thus.
Now implement the manufacture method of battery of the present invention in following description.
[positive electrode]
Refer now to Fig. 3, thereby form positive electrode 11 by on the surface of positive electrode collector 11b, forming the positive electrode active substance layer 11a that comprises positive electrode active substance.Positive electrode collector 11b is by for example making such as the metal forming of aluminium (Al) paper tinsel, nickel (Ni) paper tinsel, titanium (Ti) paper tinsel, stainless steel (SUS) paper tinsel etc.
For example thereby positive electrode active substance, electric conducting material and binding agent are made positive electrode active substance layer 11a by comprising.They form cathode mix by even mixing.Cathode mix is distributed in the solvent, obtains pulp-like solution thus.At this moment, by using thickener to adjust to have predetermined viscosity.Subsequently, be coated with positive electrode collector 11b equably, and,, form positive electrode 11 thus by the dry collector 11b of vacuum desiccator in order to remove the moisture in the positive mixture with such slurry.Here positive electrode active substance, electric conducting material, binding agent and solvent are disperseed just to be enough to equably, to they mixed proportion then without limits.
As positive electrode active substance, can select manganese dioxide or fluorographite in the situation of the battery of 3V system, or can select iron sulfide in the situation of the battery of 1.5V system.For every kind of matter energy density, manganese dioxide equal 308mAh/g, fluorographite equal 860mAh/g, iron sulfide equal 890mAh/g and as the 3860mAh/g that equals of the lithium metal of comparative electrode.
As electric conducting material, for example can use material with carbon element such as carbon black, graphite, acetylene black etc.As binding agent, can use for example polyvinylidene fluoride, polyphenyl fourth rubber (SBR) etc.As solvent, for example can use ethanol etc.
Can form positive electrode active substance layer 11a by mold pressing coating (diecoating) method, printing transferring method, method for printing screen etc.When with regard to productive rate and equipment cost consideration, a surface of active material coating metal paper tinsel is only used in expectation.Promptly, in situation with two surfaces of active material coating, in order to carry out manufacturing step by machine of use, then need the dry electrode that on a surface, prints and the step of the described electrode of winding thereafter, and the step that is coated with the back side, dry described electrode and twines described electrode with active material once more; Or in the situation that is coated with the front and the back side by consecutive steps, wherein just be coated with a surface and dry this active material with active material after, with the active material coating back side and dry and winding electrode; As the equipment of coating active material, need be used for front surface and two equipment that are used for the back side and constitute by one, cost extremely rises.In order to solve above problem, print by single (side) and to construct electrode, productive rate can be improved and the required cost of investment of facilities and equipment can be reduced significantly.
By positive electrode active substance layer 11a being formed in the positive electrode 11 that positive electrode collector 11b makes, positive electrode terminal 14 is connected to the positive electricity end part by spot welding, ultrasonic bond etc.Though expectation uses metal forming as positive electrode terminal 14, it is not limited to metal and can uses another material, as long as it is an electrochemistry and chemically stable and can make its conduction.For example, can be with the material as positive electrode terminal such as aluminium.
[negative electrode]
As negative electrode 12, use lithium metal or lithium metal alloy (in the situation that specifically is not limited to lithium metal or lithium metal alloy, it can suitably be called " lithium ").Mode with similar to positive electrode 11 in negative electrode 12, also is connected to end parts by spot welding, ultrasonic bond etc. with negative electrode terminal 15.Though expectation uses metal forming as negative electrode terminal 15, it is not limited to metal and can uses another material, as long as it is an electrochemistry and chemically stable and can make its conduction.For example, can use copper (Cu), nickel, stainless steel, with the material as negative electrode terminal such as the stainless steel of nickel coating or iron (Fe).
[spacer body]
[electrolyte solution]
As the organic solvent of electrolyte solution, can in Merlon, ethylene carbonate, butylene, gamma-butyrolacton, sulfolane, 3-methyl sulfolane, dimethoxy-ethane, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, select any one or multiple.
As electrolytic salt, can in lithium perchlorate, hexafluoro lithium phosphate, fluoroform lithium sulfonate, tetrafluoro lithium borate salts, lithium iodide etc., select any one or multiple.
By using above-mentioned material to form cell apparatus 20.Shown in Fig. 3 and 4,, make the surface of a lip-deep positive electrode active substance layer 11a being formed at positive electrode collector 11b face with each other with positive electrode 11 crooked three times or more times.By spacer body 13, the negative electrode of being made by lithium 12 is set between the surface that positive electrode active substance layer 11a faces.Surface by allowing positive electrode active substance layer 11a is not exposed to the outside with negative electrode 12 towards interior except edge surface.For lithium, because activity is very high and can easily absorb moisture, thus it is handled in the environment of low dew point, such as hothouse etc.But, even in such environment, absorbed the moisture that wait to produce from operator, formed the film of lithium hydroxide etc., worsened the characteristic of battery.Therefore, be very important by spacer body by rapid assembling electrode device of positive electrode and the surface that in the manufacturing step of the situation of handling negative electrode, covers negative electrode.
[manufacturing of battery]
Use the exterior material of making by the laminated film 16 of thickness to cover the cell apparatus of making as mentioned above 20, form battery 10 thus with about 100 μ m.Can use following material to be used to make up and form the laminated film 16 that battery 10 uses.
Fig. 5 has shown the example of the primary structure of laminated film 16.Metal level 21 by be clipped between skin of making by resin molding 22 and the internal layer of making by resin molding 23 (hereinafter, also claiming suitably to be sealant) have damp proof and multilayer films insulation property are made.Metal level 21 has the intensity of improving exterior material and the important function of protecting inside by the intrusion that hinders moisture, oxygen and light.Can suitably use the material as metal level 21 such as stainless steel, nickel-clad iron.With regard in light weight, extensibility, price and ease of processing, aluminium (Al) is most preferred.As needs, also can between metal level 21 and the sealant 23 and between metal level 21 and outer 22 tack coat 25 and tack coat 24 be set respectively.
Consider the aesthetic feeling, intensity, flexibility of outward appearance etc., can use nylon (Ny), polyethylene terephthalate (PET) or polyethylene (PE) as outer 22.Therefore, can be from wherein selecting and using multiple.
The most general structure of laminated film is (skin/metal forming/sealant)=(PET/Al/PE).The invention is not restricted to such combination and can use the general structure of other laminated films below any one.That is, (skin/metal forming/sealant)=Ny/Al/CPP, PET/Al/CPP, PET/Al/PET/CPP, PET/Ny/Al/CPP, PET/Ny/Al/Ny/CPP, PET/Ny/Al/Ny/PE, Ny/PE/Al/LLDPE, PET/PE/Al/PET/LDPE or PET/Ny/Al/LDPE/CPP.As mentioned above, also can use other metals except Al as metal forming naturally.
As shown in Figure 6, cell apparatus 20 is clipped between the above-mentioned laminated film 16, and with the combination of laminated film heat fusing, but staying a side is used to inject electrolyte solution.Electrolyte solution is injected battery and under reduced pressure will remain a side heat fusing, form battery shown in Figure 2 10 thus in conjunction with the air of eliminating battery as much as possible.
Because cell apparatus 20 be approach and under reduced pressure carry out the heat fusing combination, even in statu quo use laminated film 16 also not have problems.Yet, also can be molded it just to have recessed part before and to make cell apparatus 20 be encapsulated into this concave portion to use the volume in the battery effectively.
By using above-mentioned electrode foldable structure, can keep high yield.Even discharge, the consumption of lithium increases, and the negative electrode attenuation, is out of shape the outside of lamination by the pressure differential between interior and outer, also can prevent the reducing of contact area between positive electrode and the negative electrode.So, can eliminate the deterioration of battery behavior and supply with big electric current up to the discharge end.
By using following method, can obtain to have the battery of outstanding productive rate and Geng Gao battery behavior.
For example, make it than the thicker and formation battery in the correlation technique, can improve battery capacity by forming positive electrode active substance.But, in such situation, when meander electrode, peeling off or coming off of active material taken place.Therefore, for example, using its thickness to be equal to or greater than the situation of the thick electrode of 100 μ m, electrode that just must the lamination bar shaped.
But the situation at the electrode of lamination bar shaped for the operation of control electrode and the position precision of electrode, needs the step of load, makes productive rate low.
Therefore, as shown in Figure 7, be provided with uncoated non-applying area 36a of positive electrode active substance that positive electrode active substance arranged and 36b etc. for sweep, crooked positive electrode 31 and form battery makes the occurrence frequency such as the defective of coming off of positive electrode active substance etc. reduce thus.The non-coated portion 36a of positive electrode active substance is the non-coated portion of mountain Zhe method that is bent, and makes the positive electrode active substance layer be positioned at the outside.The non-coated portion 36b of positive electrode active substance is that the non-coated portion of paddy Zhe method that is bent makes the positive electrode active substance layer be positioned at the inboard.
If printing keeps its tension force simultaneously as the metal forming of electrode collector when printing, then be preferred for continuous production so.Therefore, used the hard metal forming that is difficult to extend.So, in the situation of meander electrode, drawn metal paper tinsel hardly.
As Fig. 8 A to shown in the 8D, on collector 40, be formed with the situation that the electrode of active material layer 41 is folded by the mountain therein, be difficult to the bending of sensing (trace) metal forming with that part of extension of the outer side contacts of active material and the cracking (Fig. 8 C) of electrode has taken place.Because this collector is around as the crackle resilience of basic point, so the glass of metal forming has taken place or come off.Even in the situation of non-coated portion existence, if the width of non-coated portion is not enough, so owing to similar reason also can be peeled off.
In the situation that electrode paddy is folding, because active material is compressed at shrinkage direction, so come off or the possibility peeled off is little.But, when considering productive rate, by for this part provides non-coated portion, sweep that can clear and definite electrode.So, because when bending the position non-migration, expectation is provided with non-coated portion.In this situation, width that need non-coated portion is set to be equal to or greater than 2T (T: the value thickness of active material).If with the thickness coating less than 2T, opposite with the situation of mountain Zhe method, metal forming is difficult to the extension of sensing electrode, makes metal forming be cut open with electrode.
As shown in Figure 9, when meander electrode, also necessarily produce minimum bending radius (r) in the metal forming inboard.R=t+r (t: the thickness of metal forming; R: outer radius).The arc BC that the arc AB of the metal forming of bending is connected to the straight line portion of metal forming connects by radius (r) at least.The angle θ of arc AB equals the angle of arc BC.The line length at the center of connection arc BC and the center of sweep equals (t+2r).In this situation, the relation between such length and the outer radius R is expressed as equation:
(t+2r)cosθ＝t+r
The length that the length of arc AB equals A=(t+r) θ and arc BC equals B=r θ.
Thereupon, this partial-length corresponding to the L among Figure 10 equals
L
2＝(t+2r)
2-(t+r)
2＝2tr+3r
2
The length (M) of the straight line of the end parts of connection arc AB and arc BC can be expressed as
M
2＝2tr+4r
2
Because M
2=L
2+ r
2
As enough hour of θ, M can be roughly
M≈A+B
Therefore, M
2=(A+B)
2
So, can be expressed as
θ
2＝2r
2/(t+2r)
Therefore, because length A+B be
A+B＝{2(t+2r)r}
1/2
The width of the non-coated portion that the mountain Zhe method part that obtains is required can for
π(t+r)+{2(t+2r)r}
1/2
Figure 11 has shown the state of the sweep that suitable non-coated portion is set.By non-coated portion being provided with to such an extent that be wider than aforesaid width, positive electrode active substance becomes the sweep active material coating of no use of mountain Zhe method part, and the danger that does not exist active material to peel off or come off.
Being at least mountain Zhe method, that non-coated portion partly is set is just enough.Even, identical width need be set being the situation that mountain Zhe method part and paddy Zhe method part all are provided with non-coated portion yet.
In addition, as shown in figure 12, thereby because be provided with to such an extent that can increase response area, so expect to be provided with the positive electrode of outermost surfaces greater than inboard positive electrode greater than the width that is positioned at inboard positive electrode by the width of the positive electrode on the outermost surfaces that will be positioned at cell apparatus.
As shown in figure 13, the end parts that can also use lamination electrode wherein prevents thus that with 49 structures that bond negative electrode 12 is outstanding.
[embodiment]
Will be at following detailed description embodiments of the invention.
To mix equably and be distributed in the ethanol as the fluorographite of 80.8 mass percents of positive electrode active substance with as the acetylene black of 15.1 mass percents of electric conducting material, obtain slurry thus.Afterwards, will be as the acetylene black of binding agent mixed with 4.1 mass percents.In this situation, the carboxymethyl cellulose that is dissolved in the water is adjusted into predetermined value (200Pas) as the thickener mixing and with viscosity, obtain cathode mix thus.
The aluminium foil that will have 20 μ m is as the positive electrode collector.By cathode mix is screen-printed on the aluminium foil, form the positive electrode active substance layer.The dry positive electrode that forms as mentioned above under vacuum environment, and thereafter positive electrode is bent into as shown in figure 12 W font.Microporous barrier is set as spacer body, thereafter, lithium metal is set, form cell apparatus thus as Figure 12.In this situation, positive electrode terminal and negative electrode terminal are arranged on the adjacent surface.
The cell apparatus of making as mentioned above is clipped between the aluminium lamination press mold, in laminated film, is outerly made by PET, metal level is made by Al, and sealant made by PE, and the laminated film heat fusing is opened wide in conjunction with staying a side simultaneously.
Subsequently, the opening portion of electrolyte solution from laminated film injected.Be dissolved into by tetrafluoro lithium boric acid and make electrolyte solution in the gamma-butyrolacton 1mol/l.After injecting electrolyte solution,, form battery thus at vacuum environment lower seal opening portion.The battery that forms is as follows.
Example 1-1
Form wherein that width equals 28mm, length equals 49mm, and thickness equals the battery that 1.8mm and capacity equal 600mAh.
Example 1-2
Form wherein that width equals 15mm, length equals 60mm, and thickness equals the battery that 2.1mm and capacity equal 400mAh.
Coin shape battery in the correlation technique is used as comparative example.Following battery is used as comparative example.
Comparative example 1-1
Used and wherein used manganese dioxide, use lithium as negative electrode, and capacity has equaled the coin shape battery CR2450 of 600mAh as positive electrode.
Comparative example 1-2
Used and wherein used fluorographite, use lithium as negative electrode, and capacity has equaled the coin shape battery CR2450 of 550mAh as positive electrode.
Comparative example 1-3
Used and wherein used manganese dioxide, use lithium as negative electrode, and capacity has equaled the coin shape battery CR1620 of 75mAh as positive electrode.
The specification that in following table 1, has shown the battery of embodiment and comparative example.
Table 1
| Capacity (mAh) | Internal resistance (Ω) | Positive electrode area (cm 2) | Cell thickness (mm) | Cell diameter (mm) | Cell widths (mm) |
| Example 1-1 | 600 | 1.2 | 4500 | 1.8 | - | 28 |
| Example 1-2 | 400 | 2.1 | 3000 | 2.1 | - | 15 |
| Comparative example 1-1 | 600 | 5.6 | 280 | 5.0 | 24 | - |
| Comparative example 1-2 | 550 | 9.7 | 280 | 5.0 | 24 | - |
| Comparative example 1-3 | 75 | 7.9 | 125 | 2.0 | 16 | - |
As also understanding like that from table 1, according to the battery that forms by the present invention, with the coin shape battery relatively, cell thickness is extremely thin and can be implemented as 15 times of the positive electrode response area of the coin shape battery or more big positive electrode response area.Because internal resistance is very little, can also prevent the deterioration of load characteristic.
Use above battery, and measured each closed circuit voltage (CCV) of the interdischarge interval of 10mA under-40 ℃ environment.Made for each battery discharge degree of depth (DOD) and to have measured and in measurement after initial 0.1 second the delay of discharge.
Figure 14 has shown the measurement result of CCV.The characteristic that has shown example 1-1 by the curve 51 of solid line demonstration.The characteristic that has shown comparative example 1-1 by the curve 52 of dotted line demonstration.The characteristic that has shown comparative example 1-2 by the curve 53 of dotted line demonstration.Even be appreciated that under-40 ℃ adverse circumstances, also can be used the dark battery discharge degree of depth (DOD) effectively by the battery that enforcement the present invention forms always, and in addition, compare with the button cell in the correlation technique, the CCV at 0% DOD place has also improved 200 to 600mV.
The measurement of peeling off and coming off of active material.
[manufacturing of battery]
Battery material and the manufacture method similar have been used, except only being provided with the non-coated portion of active material for a surface of the sweep of positive electrode by silk screen printing to aforesaid embodiment 1.It is as follows to set example and comparative example.
Example 2-1
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the outside (mountain Zhe method) that 0.15mm and non-coated portion are positioned at sweep.
Example 2-2
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the outside that 0.90mm and non-coated portion are positioned at sweep.
Example 2-3
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the outside that 1.20mm and non-coated portion are positioned at sweep.
Example 2-4
On aluminium foil, formed positive electrode active substance with 0.50mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the outside that 1.20mm and non-coated portion are positioned at sweep.
Example 2-5
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the inboard (paddy Zhe method) that 0.90mm and non-coated portion are positioned at sweep.
Example 2-6
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the inboard that 1.20mm and non-coated portion are positioned at sweep.
Example 2-7
On aluminium foil, formed positive electrode active substance with 0.50mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the inboard that 1.20mm and non-coated portion are positioned at sweep.
Comparative example 2-1
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.Do not form the non-coated portion of active material at sweep.
Comparative example 2-2
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the outside that 0.10mm and non-coated portion are positioned at sweep.
Comparative example 2-3
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.Do not form the non-coated portion of active material at sweep.
Comparative example 2-4
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the inboard that 0.10mm and non-coated portion are positioned at sweep.
Comparative example 2-5
On aluminium foil, formed positive electrode active substance with 0.30mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the inboard that 0.40mm and non-coated portion are positioned at sweep.
Comparative example 2-6
On aluminium foil, formed positive electrode active substance with 0.50mm thickness with 20 μ m thickness.With the width setup of non-dispensing area is the inboard that 0.40mm and non-coated portion are positioned at sweep.
For above-mentioned example and the battery in the comparative example, after forming battery, their are decomposed and measured peeling off and coming off of active material.In following table 2, shown measurement result.Formed ten batteries and measured the quantity of the battery that has wherein occurred peeling off or come off for each example and comparative example.
Table 2
| Collector thickness (μ m) | Active material thickness (mm) | Active material thickness x2 (mm) | Non-coated portion width (mm) | Bending direction | Peel off (quantity) | (quantity) comes off | |
| Example 2-1 | 20 | 0.3 | 0.6 | 1.50 | |
0 | 0 |
| Example 2-2 | 20 | 0.3 | 0.6 | 0.90 | |
0 | 0 |
| Example 2-3 | 20 | 0.3 | 0.6 | 1.20 | |
0 | 0 |
| Example 2-4 | 20 | 0.5 | 1.0 | 1.20 | |
0 | 0 |
| Example 2-5 | 20 | 0.3 | 0.6 | 0.90 | |
0 | 0 |
| Example 2-6 | 20 | 0.3 | 0.6 | 1.20 | |
0 | 0 |
| Example 2-7 | 20 | 0.3 | 0.6 | 1.20 | |
0 | 0 |
| Comparative example 2-1 | 20 | 0.3 | 0.6 | 0 | |
10 | 8 |
| Comparative example 2-2 | 20 | 0.3 | 0.6 | 0.10 | |
10 | 6 |
| Comparative example 2-3 | 20 | 0.3 | 0.6 | 0 | |
1 | 0 |
| Comparative example 2-4 | 20 | 0.3 | 0.6 | 0.10 | |
1 | 9 |
| Comparative example 2-5 | 20 | 0.3 | 0.6 | 0.40 | |
0 | 7 |
| Comparative example 2-6 | 20 | 0.5 | 1.0 | 0.40 | |
0 | 10 |
Be appreciated that by partly providing the non-coated portion of preset width can prevent peeling off of active material to Yushan Hill Zhe method and coming off from above result.Be appreciated that also by width partly is provided for paddy Zhe method be the twice or the more non-coated portion of thickness of the active material layer of coating, can prevent peeling off and coming off of active material.
Will be wherein as the above-mentioned crooked and stacked cell apparatus outer enclosure of electrode with laminated film, thus battery can be made with outstanding characteristic.Wherein only be coated with the structure on a surface of collector because used, so also improved productive rate with active material.In addition, by thickening the positive electrode active substance layer and the non-coated portion of suitable active material being set, can obtain to have the outstanding battery of high yield.
Battery with above structure can also be used as second embodiment.
Among first embodiment, in the situation of using lithium metal or lithium metal alloy self as the battery structure of negative electrode, the negative electrode that has produced as fruit part is extremely consumed the then separated problem of negative electrode as the aforementioned.
For the lithium battery by manganese dioxide lithium battery and the representative of fluorographite lithium battery, lithium carries out along with discharge and is consumed, and following reaction takes place.
The manganese dioxide lithium battery:
MnO
2+Li→Li/MnO
2
The fluorographite lithium battery:
(CF)n+Li→nLiF+nC
Lithium self is a kind of active material with outstanding conductance.In the battery that uses the sheet lithium electrode, if the reaction of electrode is that then lithium is consumed equably uniformly.Therefore, big problem can not take place.But,, then produce the problem that the negative electrode of part is extremely consumed if to be part uneven or it is unbalanced to occur for active material in being applied to the pressure of electrode.
In JP-A-11-54135, a kind of manufacture method that can solve the battery of following problem is disclosed.Promptly, be formed in the battery by the negative electrode of the collector of making such as the alkali metal of lithium etc. or its alloy having active material layer wherein, the negative electrode of part is consumed to heavens, and the conduction between collector and the active material is difficult to be held, and discharge voltage sharply descends.
According to the JP-A-11-54135 invention disclosed, the formation positive electrode makes positive electrode electrically conductive core body is exposed to positive electrode surface.Therefore, finish the voltage drop in the time of to prevent to discharge end up to discharge by exoelectrical reaction that postpones this part wittingly and the conduction that keeps negative electrode.
The battery of first embodiment as shown in Figure 7 has so structure, i.e. peeling off and come off for the positive electrode active substance layer 31a of the sweep that prevents positive electrode 31, be provided with non-coated portion 36a of positive electrode active substance and 36b, and at the crooked positive electrode 31 of these parts.
To shown in the 15D, in the situation that the non-coated portion of active material is formed into collector, from the angle of productive rate, expectation is printed arbitrary shape by using silk screen printing as Figure 15 A.Silk screen printing is a kind of method, and its mask 62 that will form arbitrary shape is formed on the workpiece 61 and by use blade coating device slurry 64 is printed onto on the workpiece 61.When forming positive electrode, mask is set and print active material just enough for this part of non-coated portion for planning on the collector.
But the print surface that is obtained by silk screen printing becomes the wherein shape of recessed core, shown in Figure 15 C and 15D.Thereby cause so recessed shape on the mask 62 by printing simultaneously blade coating device 63 to be pressed onto.Because the viscosity that needs to increase active material self is not come level and smooth print surface by evening up active material itself to be coated with thick active material after printing, so caused so recessed shape yet.Therefore, the part (end parts of positive electrode active substance layer) that contacts with the mask edge surface is than core height.
Figure 16 has shown the battery structure that has the battery that the electrode of shape like this forms by use.The discharge that Figure 17 has shown battery is state midway.Figure 18 has shown the discharge done state of battery.Initial in discharge is that uniform lithium negative electrode is consumed from the part of facing the end parts that is coated with positive electrode active substance.Along with discharge is carried out, lithium negative electrode 72 is changed into lithium negative electrode 72a, as shown in figure 17.Further, when the end of discharge, the lithium of facing this part of the end parts that is coated with positive electrode active substance is further consumed and is taken place the separation of lithium, lithium negative electrode 72b as shown in figure 18.In Figure 16 to 18, positive electrode and lithium negative electrode are illustrated as thick electrode, this makes can easily understand the state that lithium separates.Illustrate the structure that lithium negative electrode 72 is separated the body encapsulation.
The part that when the end of discharge discharge is worked only is the part of conducting electricity with negative electrode terminal 75.If the separation of lithium negative electrode 72 takes place, then response area extremely reduces, and makes the rapid deterioration of load characteristic or reducing of discharge capacity take place.Because the lithium negative electrode 72 that separates is non-conductive and in statu quo keeps, consider that also it enters the situation of labile state when abandoning etc.But, with regard to limited size and fail safe, during battery, compare, thereby be difficult to take to prevent the precautionary measures of the separation of lithium negative electrode 72 by excessively inserting lithium negative electrode 72 with positive electrode 71 in design.
Therefore, in a second embodiment, by allowing negative electrode to have this a kind of structure, wherein the pressurization of lithium metal or lithium metal alloy is attached to two surfaces of metal forming, metal forming has the collecting function and the support function of electrode, even the consumption state generation at lithium when discharge finishes is unbalanced, lithium does not also separate and can prevent reducing of active region.
Now implement the manufacture method of the battery of second embodiment in following description.
[positive electrode]
The positive electrode of being made by the material that uses in first embodiment can be used as positive electrode 81.Can form positive electrode active substance layer and the non-coated portion of positive electrode active substance to the method for printing screen shown in the 15D by using Figure 15 A.Part positive electrode active substance of no use coating by using mask not have with the electrode that is bent has prevented the generation of peeling off and coming off of active material thus.Sweep comprises: mountain Zhe method part, and it is bent and makes active material be positioned at the outside; With paddy Zhe method part, it is bent and makes active material be positioned at the inboard.Though expectation partly is provided with non-coated portion for each mountain Zhe method part and paddy Zhe method, by at least Yushan Hill Zhe method partly being provided with non-coated portion, can improve productive rate.
[negative electrode]
As negative electrode 82, used by lithium metal or lithium metal alloy (in the situation that specifically is not limited to lithium metal or lithium metal alloy, it suitably is called " lithium ") 82a pressurization being attached on the negative electrode collector that is made of metal and the negative electrode that obtains.As the material that is used for negative electrode collector 82b, can use a kind of for example material of nickel (Ni), titanium (Ti) and copper (Cu) that is selected from, maybe can use following material: by make the alloy of acquisition as this material of base material such as stainless steel etc.; Nickel-clad iron or stainless steel; The clad material of iron or stainless steel and nickel etc.Because the material such as aluminium, magnesium (Mg) etc. than lithium electrochemical difference becomes alloy, it is difficult to be used as negative electrode collector 82b.
Rolling paper tinsel or electrolyte paper tinsel also can be used as negative electrode collector 82b.For shape; expectation forms such shape with negative electrode collector 82b; make the part or all of surface of the negative electrode collector 82b of lithium 82a pressure combination is opened by punch die or etching, or be opened for pattern form, or preferably use the metal that extends.The vertical and horizontal width setup of negative electrode collector 82b is equal to or less than the pressurized vertical and horizontal width that is attached to the lithium 82a of negative electrode collector 82b.
Figure 19 and 20 has shown the preferred shape of negative electrode collector 82b.As shown in figure 19, can use wherein structure with the integrally formed negative electrode terminal 84 of negative electrode collector.As shown in figure 20, also can use wherein and wait the structure that negative electrode terminal 84 is connected to the end parts of negative electrode collector 82b by spot welding, ultrasonic bond.Can select the shape of employed expectation according to purpose.In that negative electrode terminal 84 and its situation of welding are set respectively, preferably use metal forming as negative electrode terminal 84.But terminal 84 is not limited to metal and can uses any materials, if its be electrochemistry and chemically stable and be the conduction.As the material of negative electrode 84, can use and utilize copper, nickel, stainless steel, nickel plating stainless steel or iron etc.
Use the reason of aforementioned shapes to be to have improved the bonding of lithium 82b for negative electrode collector 82b by the surface roughness of opening part that is formed at negative electrode collector 82b.Not only improve the bonding between lithium 82a and the negative electrode collector 82b but also improved the bonding that is arranged between the negative electrode collector 82b two lip-deep two lithium 82a, thus the negative electrode 82 that has obtained to have high reliability.In addition, can reduce the weight of negative electrode collector 82b.The area of not general requirements negative electrode collector 82b equals the area of lithium 82a.For example, if the position that lithium 82a is consumed is that significantly so preferably negative electrode collector 82b is arranged on the detaching direction of lithium 82a.
[spacer body]
Can be used as spacer body 83 similar in appearance to the employed spacer body of first embodiment.
[electrolyte solution]
Can be used as electrolyte solution similar in appearance to the employed electrolyte solution of first embodiment.
[manufacturing of cell apparatus]
Will be by positive electrode 81 crooked three that the above-mentioned non-coated portion of positive electrode active substance layer form or more times be set, make positive electrode active substance layer 81a face with each other, as shown in figure 21, and form cell apparatus 80 and make negative electrode 82 be arranged between the positive electrode active substance layer 81a by spacer body 83.In this situation, also can twine negative electrode 82 to encapsulate negative electrode 82 or always need not encapsulate it by the spacer body among Figure 21 83.
[manufacturing of battery]
Further, the exterior material coating as cell apparatus 80 usefulness of above-mentioned formation are made by laminated film 86 forms battery 90 thus.Can be used as the laminated film 86 that is used to make battery 90 similar in appearance to the employed laminated film of first embodiment.
In mode, cell apparatus 80 is clipped between the above-mentioned laminated film 86 and with the laminated film heat fusing is used to inject electrolyte solution in conjunction with staying a side simultaneously similar in appearance to Fig. 6 of first embodiment.Electrolyte solution injected battery and with the heat fusing combination under reduced pressure of a remaining side,, make thus and have similar in appearance with Fig. 2 to eliminate the air in the battery as much as possible.
State when Figure 22 has shown by the discharge end of the cell apparatus 80 that uses negative electrode collector 82b manufacturing.Using so situation of cell apparatus 80, though when discharge finishes, in the consumption state of lithium 82a, take place unbalanced because lithium 82a connects by negative electrode collector 82b, so can prevent reducing of response area.Can obtain wherein not take place the battery that discharge voltage descends and capacity reduces.
[embodiment]
Will be at the example of following detailed description second embodiment.
The measurement of load characteristic
[manufacturing of battery]
To mix equably and be dispensed in the ethanol as the fluorographite of 80.8 mass percents of positive electrode active substance with as the acetylene black of 15.1 mass percents of electric conducting material, obtain slurry thus.Afterwards, will be as the acetylene black of binding agent mixed with 4.1 mass percents.In this situation, the carboxymethyl cellulose that is dissolved in the water is adjusted into predetermined value (200Pas) as the thickener mixing and with viscosity, obtain cathode mix thus.
The aluminium foil that will have 20 μ m is as the positive electrode collector.By cathode mix is screen-printed on the aluminium foil, form the positive electrode active substance layer.The dry positive electrode that forms as mentioned above under vacuum environment, and thereafter positive electrode is bent into as shown in figure 21 W font.Microporous barrier is set as spacer body, thereafter, lithium metal is set, form cell apparatus thus as Figure 21.
The cell apparatus of making as mentioned above is clipped between the aluminium lamination press mold, in laminated film, is outerly made by PET, metal level is made by Al, and sealant made by PE, and the laminated film heat fusing is opened wide in conjunction with staying a side simultaneously.
Subsequently, the opening portion of electrolyte solution from laminated film injected.Be dissolved into by tetrafluoro lithium boric acid and make electrolyte solution in the gamma-butyrolacton 1mol/l.After injecting electrolyte solution, at vacuum environment lower seal opening portion, form test battery thus, wherein width equals 15mm, and length equals 60mm, and thickness equals 2.3mm, and capacity equals 400mAh.
The negative electrode that is used for test battery is as follows.
Example 3-1
Used the negative electrode 82 that wherein lithium metal 82a pressurization is attached to negative electrode collector 82b as shown in figure 23.The stamped metal that use is made by nickel is as the negative electrode collector, and wherein width equals 20mm, and length equals 30mm, and thickness equals 20 μ m.And will be wherein width equal lithium metal pressure that 28mm and length equals 50mm and be attached in two surfaces each, form negative electrode thus.
Comparative example 3-1
As shown in figure 24, do not use the negative electrode collector, and use lithium metal 72 as negative electrode.Lead-in wire 75 pressure of being made by nickel that will serve as terminal are attached to width wherein and equal the lithium metal that 28mm and length equal 50mm, form negative electrode thus.
Use the test battery of as above making, and measured their load characteristic.The load of 2.7k Ω is applied to test battery and carries out discharge continuously.In Figure 25, shown measurement result.
In Figure 25, by the voltage among the curve indication example 3-1 of solid line demonstration, by the voltage among the curve indication comparative example 3-1 of dotted line demonstration.According to the battery of example 3-1, finish not exist discharge undesired up to discharge.According to the battery of comparative example 3-1, there is a rapid voltage drop in the moment near 300 hours after discharge, and also has rapid voltage drop 340 hours the moment.
After continuous discharge finishes, the test battery of comparative example 3-1 is decomposed and has confirmed the state of battery.So, determined that the voltage drop among the separated and comparative example 3-1 of the lithium metal of negative electrode is that reducing by response area causes.
As above-mentioned, in the situation of using lithium metal or lithium metal alloy as negative electrode, be made of metal and support the collector of negative electrode by setting, the separation of lithium can be prevented, and the deterioration of the load characteristic when discharge finishes can be prevented.
Battery with following structure also can be used as the 3rd embodiment.
In battery with such electrode structure, wherein a surface coated of collector has active material and first and second embodiment are crooked and be provided with as the aforementioned with synthetic collector, in the situation that electrode terminal is welded to electrode, thereby for example welded sheet metal by electric resistance welding or ultrasonic bond.But, as shown in figure 26, in first and second embodiment, positive electrode active substance 91a is formed into the end parts of positive electrode collector 91b and positive electrode terminal 94 is welded to the back side of the part that is formed with positive electrode active substance 91a.Therefore, be welded with heat or vibration damage that the positive electrode active substance of part of positive electrode terminal 94 produces when soldered, make coming off of positive electrode active substance etc. taken place.Therefore, exist to take place that discharge capacity reduces and the active material that comes off is inserted into and penetrates spacer body during the assembled battery device, thereby the possibility of internal short-circuit takes place.
Though being coated with the positive electrode collector 91b of positive electrode active substance 91a is extremely thin metal forming, collector self does not have little resistance.And have such problem, if positive electrode terminal 94 is welded to the edge surface of positive electrode collector 91b, then the electric current of collecting from other edge surfaces, caused loss by the resistance of electrode terminal 94 parts.
Therefore, in the 3rd embodiment, the end parts by the non-coated portion of positive electrode active substance being formed into positive electrode and with the positive electrode terminal adhere to this part, prevented coming off of the positive electrode active substance that when the adhere positive electrode, causes etc.One end parts of positive electrode is overlapped onto the other end part of positive electrode to cover negative electrode and to electrically contact with it.
Now implement the manufacture method of the battery of the 3rd embodiment in following description.
Figure 27 has shown the structure of implementing battery 100 of the present invention.According to battery 100, the crooked positive electrode 101 that wherein is formed with positive electrode active substance layer 101a on positive electrode collector 101b makes positive electrode active substance layer 101a face mutually.By spacer body 103, the negative electrode 102 that wherein is formed with negative electrode active material 102a on two surfaces of negative electrode collector 102b is set in the part that positive electrode active substance layer 101a faces with each other, and entire cell device laminated film 106 outer enclosure.Sweep for positive electrode is provided with non-coated portion 107a of positive electrode active substance layer and 107b.Positive electrode terminal is welded to the end parts of positive electrode collector 101b.This end parts contacts with encapsulation negative electrode 102 with the other end branch of positive electrode collector.Positive electrode terminal 104 and negative electrode terminal 105 are drawn the bound fraction of the laminated film 106 of unit, battery top (not shown).
Now implement the manufacture method of battery of the present invention in following description.
[positive electrode]
The positive electrode of being made by employed material in first and second embodiment can be used as positive electrode 101.Can be by using the non-coated portion of positive electrode active substance that forms the sweep setting of positive electrode similar in appearance to the method for printing screen of second embodiment.Sweep comprises: mountain Zhe method part, and it is bent and makes positive electrode active substance be positioned at the outside; With paddy Zhe method part, it is bent and makes positive electrode active substance be positioned at the inboard.By at least Yushan Hill Zhe method partly being provided with the non-coated portion of positive electrode active substance, can improve productive rate.
In this situation, also non-coated portion 108 as shown in figure 28 is formed into the positive electricity end part by the method that mask etc. is set.Subsequently, positive electrode terminal is welded to non-coated portion 108 by spot welding, ultrasonic bond etc.Because have the material that the material of outstanding conductance is used as positive electrode collector 101b, use the ultrasonic bond of coupling metallic molecule better than the electric resistance welding that uses contact resistance.
[negative electrode]
As negative electrode 102, can use the negative electrode that employed material and structure are made in second embodiment.Though lithium metal or lithium metal alloy can be used to negative electrode 102, have such risk, wherein lithium is consumed when discharge unevenly, from the position that consumption is carried out lithium separates and cause battery behavior when discharge finishes rapid deterioration takes place.In order to solve such problem, shown in Figure 23 as second embodiment used a kind ofly by lithium 102 pressurizations being attached to the structure of negative electrode collector 102b, even lithium separates and takes place so, also can guarantee conduction.Can use any one shape shown in Figure 19 and 20 as negative electrode collector 102b.
[spacer body]
Spacer body similar in appearance to the use of first and second embodiment can be used as spacer body 103.
[electrolyte solution]
Can be used as electrolyte solution similar in appearance to the employed electrolyte solution of first and second embodiment.
[manufacturing of cell apparatus]
Material forms cell apparatus by using so.As shown in figure 29, with positive electrode 101 crooked three or more times, make the surface that is formed at positive electrode collector 101b one lip-deep positive electrode active substance layer 101a face.By spacer body 103,, form cell apparatus 110 thus in that the negative electrode that wherein lithium 102a pressurization has been attached on the negative electrode collector 102b is set between the surface that positive electrode active substance layer 101a faces.In this situation, as shown in figure 27, adhere has the positive electrode collector end part of positive electrode terminal 104 also can contact with the other end of positive electrode collector with covering negative electrode 102 and with being with 109 to fix.So, form cell apparatus 110 as shown in figure 30.
[manufacturing of battery]
Exterior material coating as cell apparatus 110 usefulness of above-mentioned formation are made by the laminated film 106 with about 100 μ m thickness forms battery 100 thus.Can be used as the laminated film 106 that is used to make battery 100 similar in appearance to the employed laminated film of first and second embodiment.
As shown in figure 31, cell apparatus 110 is clipped between the above-mentioned laminated film 106 and the combination of laminated film heat fusing is stayed a side simultaneously and be used to inject electrolyte solution.Electrolyte solution is injected battery and will remain side heat fusing combination under reduced pressure to eliminate the air of battery as much as possible, manufacturing has and battery shown in Figure 32 100 thus.In battery shown in Figure 32 100, will be set at lower surface by the part of the upper surface in the situation of heat fusing combination corresponding to the laminated film 106 of cell apparatus 110 in Figure 31.
[embodiment]
Will be at following detailed description example of the present invention.
The measurement of peeling off and coming off of active material
[manufacturing of battery]
To mix equably and be dispensed in the ethanol as the fluorographite of 80.8 mass percents of positive electrode active substance with as the acetylene black of 15.1 mass percents of electric conducting material, obtain slurry thus.Afterwards, will be as the acetylene black of binding agent mixed with 4.1 mass percents.In this situation, the carboxymethyl cellulose that is dissolved in the water is adjusted into predetermined value (200Pas) as the thickener mixing and with viscosity, obtain cathode mix thus.
The aluminium foil that will have 20 μ m is as the positive electrode collector.By cathode mix is screen-printed on the aluminium foil, form the positive electrode active substance layer.The dry positive electrode that forms under vacuum environment.
By ultrasonic bond positive electrode terminal is welded to the positive electrode collector that has been formed with on it as above-mentioned positive electrode active substance layer, forms positive electrode thus.As follows at the electrode that this situation forms.
Example 4-1
A surface that is coated with the positive electrode collector with positive electrode active substance makes sweep positive electrode active substance of no use be coated with.The non-coated portion that has the 5mm width for edge surface being provided with of positive electrode collector, dry positive electrode, and width is wherein equaled 4mm and thickness thereafter, and equal the back side of the fin adhere made of aluminum of 0.8mm to the non-coated portion of gate electrode active material of positive electrode collector edge surface.
Comparative example 4-1
A surface that is coated with the positive electrode collector with positive electrode active substance makes sweep positive electrode active substance of no use be coated with.After dry positive electrode, width is wherein equaled 4mm and thickness equals the back side of the fin adhere made of aluminum of 0.8mm to the non-coated portion of gate electrode active material of positive electrode collector edge surface.
Every kind for above-mentioned example 4-1 and comparative example 4-1 has formed 20 positive electrodes.The appearance that comes off of active material and not occurring when determining the welding of sheet metal.Measured the quantity of the electrode that comes off.
The affirmation result who comes off who in following table 3, has shown active material.
Table 3
| The quantity of the battery of measuring | Quantity with electrode that active material comes off | |
| Example 4-1 | 20 | 0 |
| Comparative example 4-1 | 20 | 15 |
From above result,, can determine not have coming off and being improved effect of active material when not when the dorsal part of positive electrode terminal adhere part forms active material layer.
Embodiment 5
The measurement of battery behavior
Subsequently, crooked positive electrode makes the positive electrode active substance layer face with each other.Microporous barrier is set to spacer body.Afterwards, the negative electrode that will have structure as shown in figure 23 is arranged between the positive electrode active substance layer, forms cell apparatus thus.In this situation, positive electrode terminal and negative electrode terminal are set to adjacent surface.
To be clipped in wherein exterior layer as the cell apparatus of above-mentioned formation and make by PET, between the aluminium lamination press mold that metal level is made by Al and sealant is made by PE, and with the laminated film heat fusing in conjunction with staying a side simultaneously.
Subsequently, the opening portion of electrolyte solution from laminated film injected.Be dissolved into by tetrafluoro lithium boric acid and make electrolyte solution in the gamma-butyrolacton 1mol/l.After injecting electrolyte solution,, form battery thus at vacuum environment lower seal opening portion.The battery that forms is as follows.
Example 5-1
Used the positive electrode that the non-coated portion of positive electrode active substance is set for an end parts.The positive electricity end that is welded with positive electrode terminal is overlapped the other end part of positive electrode to cover negative electrode, they are fixing with band, form cell apparatus thus.This cell apparatus laminated film outer enclosure forms battery thus.
Comparative example 5-1
Used the positive electrode that the non-coated portion of positive electrode active substance is set for an end parts of positive electrode 11.As shown in figure 33, with adhere to the positive electrode terminal 104 of the edge surface of positive electrode 111 with first embodiment in the side fold back in the opposite direction, and with being with 119 to fix, and do not make positive electrode terminal 104 other edge surface conductions for positive electrode 111, form cell apparatus thus.This cell apparatus laminated film outer enclosure forms battery thus.
Every kind of internal resistance that forms battery and measure every kind of battery for above-mentioned example 5-1 and comparative example 5-1.
The measurement result of mean value that in following table 4, has shown the internal resistance of battery.
Table 4
| The quantity of the battery of measuring | Average internal resistance (Ω) | |
| Example 5-1 | 10 | 1.68 |
| Comparative example 5-1 | 10 | 2.20 |
From above result, confirmed that edge surface by allowing the positive electrode collector is overlapping and make their conductions with other edge surfaces, reduced the internal resistance of battery, the feasible characteristic that can improve battery.
By for the positive electrode collector end the non-coated portion of positive electrode active substance being set partly, can preventing to work as coming off of adhere positive electricity end period of the day from 11 p.m. to 1 a.m active material, and can keep high yield and high battery capacity as above-mentioned.Make up cell apparatus by making the end parts of positive electrode collector contact, can reduce internal resistance and can improve battery behavior with the other end of collector.
Though in the above the preferred embodiments of the present invention that specifically described, the invention is not restricted to aforesaid embodiment, and be possible based on many changes and improvements of technical conceive of the present invention.
For example, mentioned numerical value as an example in the foregoing embodiments, and as need also can use other numerical value different with them.
Cell apparatus also can use the structure with polymer dielectric.
One skilled in the art should appreciate that according to design needs and other factors, can produce various improvement, combination, sub-portfolio and replacement, as long as they drop in the scope of claim or its equivalent.
The theme that Japanese patent application 2004-334794 number that the present invention relates to submit on November 18th, 2004, the Japanese patent application of submitting on November 18th, 2004 2004-334795 number and the Japanese patent application submitted on February 7th, 2005 are 2005-030096 number, the full content of these applications is incorporated herein by reference.
Claims (10)
1, a kind of battery comprises:
Positive electrode, wherein the positive electrode active substance layer is formed on the positive electrode collector of being made by the bullion paper tinsel;
Negative electrode is made by lithium metal or lithium metal alloy; With
Spacer body,
Wherein, the described positive electrode collector of being made by the bullion paper tinsel is formed on described spacer body one side, described positive electrode active substance layer is formed at a side of the described positive electrode collector of being made by the bullion paper tinsel, make described positive electrode active substance layer between positive electrode collector and spacer body, and
Described negative electrode is arranged at the opposite side of described spacer body;
The spacer body bending that will have described positive electrode, negative electrode makes described positive electrode collector face with each other;
Wherein, described positive electrode active substance layer is a fluorographite;
The non-coated portion of described positive electrode active substance layer is formed in the sweep of described positive electrode;
The thickness of described positive electrode active substance layer is equal to or greater than 100 μ m and is equal to or less than 500 μ m;
At least Yushan Hill Zhe method partly is provided with the non-coated portion of described positive electrode active substance;
The width of described positive electrode that is positioned at outermost surfaces is greater than the width that is arranged at the positive electrode on the inner surface.
2, battery according to claim 1, wherein,
With entire cell device laminated film outer enclosure, in described laminated film, the outer surface and the inner surface of metal level are clipped between the resin bed, and
The negative electrode terminal that is electrically connected to the positive electrode terminal of described positive electrode and is electrically connected to described negative electrode is drawn the adhesive segment of described laminated film.
3, battery according to claim 1, wherein, the width of the non-coated portion of described positive electrode active substance that partly is provided with for described mountain Zhe method is equal to or greater than
π(t+r)+{2(t+2r)r}
1/2
Wherein,
T: the thickness of described positive electrode collector;
R: the radius of sweep that is formed at the inboard of described positive electrode collector.
4, battery according to claim 1 is characterized in that,
Described negative electrode is by forming on two surfaces that the pressurization of described lithium metal or described lithium metal alloy are attached to the negative electrode collector.
5, battery according to claim 4, wherein, an end parts of described positive electrode contacts to cover described negative electrode with the other end of described positive electrode branch.
6, battery according to claim 5, wherein,
For the end parts on the surface of the described positive electrode that is formed with described positive electrode active substance layer the non-coated portion of described positive electrode active substance is set, and
Positive electrode terminal is connected to the back side of described non-coated portion or described non-coated portion.
7, battery according to claim 4, wherein, the vertical and horizontal width of described negative electrode collector is equal to or less than by the vertical and horizontal width of the described lithium metal of pressure combination or described lithium metal alloy.
8, battery according to claim 4, wherein, the part or all of surface of the described negative electrode collector of described lithium metal or the combination of described lithium metal alloy pressure has opening.
9, battery according to claim 4, wherein, it is integrally formed to described negative electrode collector to be drawn out to outside negative electrode terminal.
10, battery according to claim 9, wherein, described negative electrode terminal is fixed in described negative electrode collector.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004334794A JP2006147300A (en) | 2004-11-18 | 2004-11-18 | Battery |
| JP334795/04 | 2004-11-18 | ||
| JP334794/04 | 2004-11-18 | ||
| JP30096/05 | 2005-02-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1776939A CN1776939A (en) | 2006-05-24 |
| CN100563048C true CN100563048C (en) | 2009-11-25 |
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|---|---|---|---|
| CN 200510120498 Expired - Fee Related CN100563048C (en) | 2004-11-18 | 2005-11-18 | Battery |
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|---|---|
| JP (1) | JP2006147300A (en) |
| CN (1) | CN100563048C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107210453A (en) * | 2015-01-26 | 2017-09-26 | 罗伯特·博世有限公司 | The design of solid state battery |
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| KR101090684B1 (en) * | 2009-07-16 | 2011-12-08 | 에스케이이노베이션 주식회사 | Electrode assembly for battery and manufacturing thereof |
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| JPWO2013098968A1 (en) * | 2011-12-27 | 2015-04-30 | 株式会社東芝 | Electrode manufacturing method and non-aqueous electrolyte battery manufacturing method |
| JPWO2013098969A1 (en) * | 2011-12-27 | 2015-04-30 | 株式会社東芝 | Electrode manufacturing method and non-aqueous electrolyte battery manufacturing method |
| EP2800173A4 (en) * | 2011-12-27 | 2015-08-05 | Toshiba Kk | Method for producing electrode and method for producing non-aqueous electrolyte battery |
| KR101586121B1 (en) * | 2013-09-30 | 2016-01-22 | 주식회사 엘지화학 | Lamination device including electrode guide |
| KR102364849B1 (en) * | 2015-06-18 | 2022-02-18 | 삼성전자주식회사 | Metal-air battery |
| CN105355918A (en) * | 2015-10-21 | 2016-02-24 | 山东精工电子科技有限公司 | Natural ferrous disulfide acid-treatment positive electrode material and preparation method thereof |
| JP7041048B2 (en) | 2018-12-13 | 2022-03-23 | 本田技研工業株式会社 | Manufacturing method of laminated battery and laminated battery |
| CN112635845B (en) * | 2020-12-22 | 2022-04-08 | 武汉昊诚锂电科技股份有限公司 | Preparation method of battery cell structure and battery cell structure |
| JP2024501547A (en) * | 2021-11-23 | 2024-01-12 | 寧徳時代新能源科技股▲分▼有限公司 | Electrode assembly and its manufacturing method, battery cell, battery and power consumption device |
-
2004
- 2004-11-18 JP JP2004334794A patent/JP2006147300A/en active Pending
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2005
- 2005-11-18 CN CN 200510120498 patent/CN100563048C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107210453A (en) * | 2015-01-26 | 2017-09-26 | 罗伯特·博世有限公司 | The design of solid state battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1776939A (en) | 2006-05-24 |
| JP2006147300A (en) | 2006-06-08 |
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