CN100508251C - Method for making lithium ion cell positive electrode sheet, positive-electrode sheet and lithium ion cell - Google Patents
Method for making lithium ion cell positive electrode sheet, positive-electrode sheet and lithium ion cell Download PDFInfo
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- CN100508251C CN100508251C CNB200510020369XA CN200510020369A CN100508251C CN 100508251 C CN100508251 C CN 100508251C CN B200510020369X A CNB200510020369X A CN B200510020369XA CN 200510020369 A CN200510020369 A CN 200510020369A CN 100508251 C CN100508251 C CN 100508251C
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- 238000000034 method Methods 0.000 title claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002562 thickening agent Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims description 68
- 229920000159 gelatin Polymers 0.000 claims description 59
- 239000008273 gelatin Substances 0.000 claims description 59
- 235000019322 gelatine Nutrition 0.000 claims description 59
- 235000011852 gelatine desserts Nutrition 0.000 claims description 59
- 108010010803 Gelatin Proteins 0.000 claims description 58
- 239000007767 bonding agent Substances 0.000 claims description 45
- 239000006258 conductive agent Substances 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 38
- 239000002202 Polyethylene glycol Substances 0.000 claims description 30
- 239000007774 positive electrode material Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 22
- 229920000126 latex Polymers 0.000 claims description 18
- 239000004816 latex Substances 0.000 claims description 18
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 18
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 18
- -1 alcohol ester Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
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- 150000001875 compounds Chemical class 0.000 claims description 10
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910014689 LiMnO Inorganic materials 0.000 claims 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
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- 238000004026 adhesive bonding Methods 0.000 abstract 2
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 39
- 239000011248 coating agent Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 30
- 239000002174 Styrene-butadiene Substances 0.000 description 28
- 229920003048 styrene butadiene rubber Polymers 0.000 description 28
- 229910012820 LiCoO Inorganic materials 0.000 description 19
- 238000001035 drying Methods 0.000 description 12
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- 235000019422 polyvinyl alcohol Nutrition 0.000 description 12
- 239000008213 purified water Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000011031 large-scale manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
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- 238000007599 discharging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007591 painting process Methods 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
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Classifications
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The method includes working procedure for preparing pulp in water phase. The procedure includes step for mixing materials i.e. mixing materials of powder particles of active material of positive pole, current conducting agent, and binding material of current conducting agent evenly to produce pulp in paste form. The binding material is in use for adhering current conducting agent onto surface of powder particles of active material of positive pole. Thickening agent and assistant binding material are added to the mixing step. The thickening agent is in use for adjusting viscosity of mixed pulp. The assistant binding material is in use for raising adhesive bonding performance, as well as improving flexibility of pole pieces. The invention also discloses method for preparing positive pole pieces and lithium ion batteries. The invention reduces influence on electrochemistry capability of battery caused by binding material utilized in aqueous adhesive bonding in current technique.
Description
[technical field]
The present invention relates to materials chemistry field and high-energy battery technology, specifically relate to a kind of based lithium-ion battery positive plate manufacture method, also relate to the positive plate of the lithium ion battery of the method manufacturing and use the lithium ion battery of this positive plate.
[background technology]
Lithium ion battery is a kind of high performance secondary cell, have operating voltage height, volume and weight energy density height, the life-span is long, self-discharge rate is low, memory-less effect and be of value to advantages such as environment, be widely used in mobile communication equipment, notebook computer, take the photograph videocorder, field such as PDA(Personal Digital Assistant), digital camera, electric tool and torpedo, guided missile.In the last few years, the lithium ion battery manufacturing technology had had very much progress, made the capacity of battery be greatly improved.But with regard to the manufacture method of battery pole piece (positive plate and negative plate), still continue to use coating process.Coating process divides oil phase coating and water to be coated with two kinds.Oil phase is coated with an organic solvent and dissolves in the bonding agent in the organic solvent, and active powder of both positive and negative polarity and conductive agent are made slurry.The water coating is a solvent with water, uses the bonding agent in the water soluble, and active powder of both positive and negative polarity and conductive agent are made slurry.In general, the water coating, cost is low, removes the problem of organic pollutants again from, is preferred coating process.At present, in large-scale production, the water coating technique has been adopted in the manufacturing of negative plate, for example uses water as solvent, makes bonding agent with sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) latex.But, when the large-scale production positive plate, generally still continue to use the oil phase coating technique.
Recently, people such as R.Dominko have proposed a kind of method (R.Dominko el al that makes positive plate by the water coating, Electrochemical and Solid-state Letters, 4 (11) A187-A190 (2001)), wherein: at first use polyelectrolyte, handle positive electrode particle to be coated as gelatin (Gelatin); Then, (Printen XE2 Degussa) allows each positive electrode particle surface deposit the carbon black particle that last layer is of a size of 0.1 μ m to add high conductive agent; At last, positive electrode particle and the collector bonding foil of gelatin, carbon black being handled with other polyelectrolyte (gelatin, cellulose etc.) made pole piece together.Because carbon black and bonding agent distribute according to qualifications, in the positive plate that this method is made, gelatin and conductive agent content can reduce widely, and it is about 96% that active component can be brought up to, and do not reduce the performance of positive plate simultaneously.But there is following defective in the method that adopts people such as R.Dominko to propose by usual large-scale production device fabrication positive plate the time: bonding force deficiency between (1) positive electrode and aluminium foil, when single face is coated with, fall to expect that phenomenon is serious especially; (2) gelatin makes the aluminium foil that is stained with anode sizing agent seem harder as bonding agent, not as Kynoar (PVDF) bonding agent softness; (3) only the qualified positive plate of surface density can not be obtained, promptly enough thick positive plate can not be obtained, because the molecular weight of gelatin low excessively (molecular weight ranges is 1-2.5 ten thousand) with gelatin.People also research and development other lithium ion battery aqueous adhesive be coated with the manufacturing battery pole piece, as acrylic acid-styrene polymer, acrylic acid-silicon-oxygen polymer, cinnamic acrylic ester polymer (JP2000294230); Styrene-butadiene polymer waterborne polymeric latexes such as (JP2000106198).This base polymer is producing certain influence to battery performance in varying degrees because of there being more emulsifying agent; This its viscosity of base polymer latex is on the low side in addition, and this is a unfavorable factor in preparation positive and negative electrode slurry and coating process process, causes the surface density of pole piece low excessively.
[summary of the invention]
The objective of the invention is to overcome the deficiency of above-mentioned positive plate manufacture method; it is effective to propose a kind of coating; be applicable to the water coating based lithium-ion battery positive plate manufacture method of large-scale production equipment, and the positive plate and the lithium ion battery with described positive plate that use this method manufacturing.
In order to achieve the above object, the technical solution used in the present invention is: a kind of based lithium-ion battery positive plate manufacture method, comprise water pulp preparation operation, comprise the step that raw material mixes in this operation, promptly, to comprise the positive electrode active materials powder, conductive agent, the raw material of conductive agent bonding agent is uniformly mixed into the paste slurry, described conductive agent bonding agent is used for conductive agent is evenly sticked to positive electrode active materials powder surface, also adds in the step that described raw material mixes to be used to adjust the thickener that mixes the gained slurry viscosity and to be used to improve the adhesive property between positive electrode and the collector and to improve the auxiliary bonding agent of pole piece flexibility.
Described thickener can be the mixture of water-soluble high-molecular compound or several water-soluble high-molecular compounds.
Described water-soluble high-molecular compound is preferably from polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyacrylamide, Sodium Polyacrylate, polyacrylic acid alcohol ester, polyvinylpyrrolidone.Wherein, particularly preferably be polyvinyl alcohol, polyethylene glycol oxide, Sodium Polyacrylate, polyacrylic acid alcohol ester.Its molecular weight is preferably, polyvinyl alcohol 50000～450000, polyethylene glycol oxide 50000～450000, Sodium Polyacrylate 50000～250000, polyacrylic acid alcohol ester 50000～150000.
Described auxiliary bonding agent can be following material or their mixture: butadiene-styrene rubber (SBR), acrylonitrile-butadiene latex, polytetrafluoroethylene (PTFE) latex.Wherein, particularly preferably be butadiene-styrene rubber.
In the above-mentioned manufacture method:
0.5～4.0% of the preferred positive electrode active materials weight of gelatin consumption.Preferred especially 1.0～3.0%.
0.1～3.0% of the preferred positive electrode active materials weight of the consumption of thickener.Preferred especially 0.5～2.0%.
0.5～6.0% of the preferred positive electrode active materials weight of consumption of auxiliary bonding agent.Preferred especially 1.0～4.5%.
Described positive electrode active materials comprises and is selected from the represented lithium compound of following chemical formula:
1)Li
xMn
1-yMyA
2
2)Li
xMn
1-yM
yO
2-zX
z
3)Li
xMn
2O
4-zX
z
4)Li
xMn
2-yM
yA
4
5)Li
xCo
1-yM
yA
2
6)Li
xCo
1-yM
yO
2-zX
z
7)Li
xNi
1-yM
yA
2
8)Li
xNi
1-yM
yO
2-zX
z
9)Li
xNi
1-yCo
yO
2-zX
z
10)Li
xNi
1-y-zCo
yM
zA
α
11)Li
xNi
1-y-zCo
yM
zO
2-αX
α
12)Li
xNi
1-y-zMn
yM
zA
α
13)Li
xNi
1-y-zMn
yM
zO
2-αX
α
Wherein: 0.95 ≦ x ≦ 1.1,0 ≦ y ≦ 0.5,0 ≦ z ≦ 0.5,0 ≦ α ≦ 2; M is selected from a kind of in Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V or the rare earth element; A is selected from O, F, S and P; X is selected from F, S and P.
The present invention and providing utilizes positive plate that above-mentioned technology makes and the lithium ion battery that contains this positive plate.
Adopt technique scheme, in conjunction with the following embodiment that will describe in detail, beneficial technical effects of the present invention is: 1) compare with other existing water-based adhesive technology, reduced use acrylic acid-styrene polymer, acrylic acid-silicon-oxygen polymer, when the cinnamic acrylic ester polymer latex is done bonding agent to the influence of battery performance; 2) use the auxiliary bonding agents of conduct such as SBR, PTFE latex to use water-soluble polymer to help and stickingly can access better pole piece adhesive effect, because the use thickener has avoided slurry rare excessively, coating performance is better simultaneously; 3) can obtain for example 425g/m of qualified surface density
2Positive plate, simultaneously pole piece is softer and not easy to break, has eliminated the defective of the pole piece serious " falling material " that produces when only making bonding agent with gelatin; 4) technology is simple, can be applicable to existing large-scale production equipment, helps industry and uses and promote; 5) lithium ion battery of the positive plate of use method manufacturing of the present invention is basic identical with the battery performance of oil phase coating usually, but adopt outside the few characteristics of method decapacitation reservation Dominko method bonding agent of the present invention and conductive agent consumption, also have and remove the advantage that oil phase method NMP (N-methyl pyrrolidone) pollutes from, and have the economic benefit of bringing without NMP.
[description of drawings]
Fig. 1 is 100 cycle performance curve charts that adopt the lithium ion battery of the positive plate of making according to the inventive method.
Fig. 2 is the discharge capacity attenuation trend figure that adopts the lithium ion battery of the positive plate of making according to the inventive method.
Fig. 3 is the discharge capacity of lithium ion battery comparison diagram that adopts the lithium ion battery of the positive plate of making according to the inventive method and adopt the positive plate of present method manufacturing.
[embodiment]
The invention provides a kind of based lithium-ion battery positive plate manufacture method, comprise pulp preparation operation and slurry painting process, it is characterized in that: comprise the step that positive electrode active materials powder, gelatin, conductive agent, thickener and auxiliary bonding agent is uniformly mixed into the paste slurry in the described pulp preparation operation, described thickener is used to adjust the viscosity that mixes the gained slurry, and described auxiliary bonding agent is used for the flexibility that collaborative gelatin improves bonding force and pole piece.
The thickener that uses can be the mixture of water-soluble high-molecular compound or several water-soluble high-molecular compounds.For example polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyacrylamide, Sodium Polyacrylate, polyacrylic acid alcohol ester, polyvinylpyrrolidone etc.Wherein, the best with one of polyvinyl alcohol, polyethylene glycol oxide, Sodium Polyacrylate, polyacrylic acid alcohol ester or their mixture as the thickener effect.These several polymer molecular weights are preferably, polyvinyl alcohol 50000～450000, polyethylene glycol oxide 50000～450000, Sodium Polyacrylate 50000～250000, polyacrylic acid alcohol ester 50000～150000.The thickener consumption is controlled at 0.1～3.0% of positive electrode active materials weight, and preferred especially 0.5～2.0%.With the viscosity of polymer as thickener scalable slurry, consumption too high (〉 3%) it is undesirable and can reduce the discharge platform of battery and the cycle performance of battery to make the solid content of the positive plate of manufacturing reduce the capacity performance that causes battery; Consumption low excessively (＜0.1%) does not have the effect of thickening, and slurry is crossed the bad control of surface density that rare meeting makes pole piece, is unfavorable for coating.The molecular weight of thickener is preferred 50,000-450,000, and it is not obvious that molecular weight is crossed low thickening effect, too highly causes that slurry is feeding-up to be unfavorable for coating equally.
The auxiliary bonding agent that uses can be following material or their mixture: butadiene-styrene rubber (SBR), acrylonitrile-butadiene latex, polytetrafluoroethylene (PTFE) latex.Wherein, particularly preferably be butadiene-styrene rubber.The consumption of auxiliary bonding agent is controlled at 0.5～6.0% of positive electrode active materials weight, preferred especially 1.0～4.5%.Use auxiliary bonding agent to use gelatin bonding more separately, can improve viscosity, and can improve the cementability of anode sizing agent and collector body and the coating performance that improves anode sizing agent, unsuitable too high (〉 6% of its consumption), the capacity performance that the too high meeting of consumption reduces the solid content of the positive plate of manufacturing and causes battery is undesirable, consumption low excessively (＜0.5%) will cause the adhesive property variation of slurry and aluminium foil, cause that easily pole piece falls material.
0.5～4.0% of the preferred positive electrode active materials weight of gelatin consumption.Preferred especially 1.0～3.0%.The consumption of gelatin very few (＜0.5%) can not make conductive agent fully uniformly attached to the surface of positive electrode, and the internal resistance of battery is excessive with causing; Consumption is (〉 4% too much), the pole piece that makes is harder and cause the pole piece solid content to reduce and then cause that the capacity of battery reduces.
The positive electrode active materials of selecting for use in the mill can comprise and is selected from chemical formula: Li
xMn
1-yM
yA
2, Li
xMn
1-yM
yO
2-zX
z, Li
xMn
2O
4-zX
z, Li
xMn
2-yM
yA
4, Li
xCo
1-yM
yA
2, Li
xCo
1-yM
yO
2-zX
z, Li
xNi
1-yM
yA
2, Li
xNi
1-yM
yO
2-zX
z, Li
xNi
1-yCo
yO
2-zX
z, Li
xNi
1-y-zCo
yM
zA
α, Li
xNi
1-y-zCo
yM
zO
2-αX
α, Li
xNi
1-y-zMn
yM
zA
α, Li
xNi
1-y-zMn
yM
zO
2-αX
αRepresented lithium compound.Wherein: 0.95 ≦ x ≦ 1.1,0 ≦ y ≦ 0.5,0 ≦ z ≦ 0.5,0 ≦ α ≦ 2; M is selected from a kind of in Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V or the rare earth element; A is selected from O, F, S and P; X is selected from F, S and P.
In the pulp preparation operation, positive electrode active materials powder, aqueous gelatin solution, conductive agent, thickener and auxiliary bonding agent mixed to adopt multiple charging sequence, they are mixed uniformly just passable as long as can look after various Material Characteristics.In mixed process, can the pH of mixture be adjusted to 7～9 with micro-alkali lye, this is because the main component amino acid of gelatin is amphoteric compound, under this environment, can make the stronger hydrogen bond of formation between the amino acid molecular, improve its bonding force, can make the more uniform surface of conductive agent during the preparation slurry, improve conductivity attached to the active anode compartment material.As its pH too high (〉 9) or low excessively (＜7) all be unfavorable for the formation of hydrogen bond, and then cause the slurry conductivity for preparing relatively poor.Adjust the preferred LiOH of alkali lye of pH,, just can and then not influence the chemical property of battery because it can not make solution bring impurity.
Below, by specific embodiment in detail realization of the present invention and effect are described in detail.In view of improvement of the present invention is the preparation section of positive plate coating sizing-agent for simplicity's sake, to omit the detailed description to the slurry painting process of routine in an embodiment.
Embodiment one, make auxiliary bonding agent, make thickener, press LiCoO with PEO with SBR
2: conductive agent: gelatin: SBR:PEO=100:2:1:1:0.5 batching.
At first the 10g gelatin is obtained gelatin solution with the 350ml dissolved in purified water, then 5g PEO (molecular weight is 250,000) is dissolved in the 350ml pure water fully, with the 350ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, the PEO solution that adds 10 gram SBR and prepare stirred 3 hours again, and then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment two, each proportioning and preparation method and embodiment one are basic identical, and just to change molecular weight into be 250,000 polyvinylpyrrolidone to thickener.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment three, make auxiliary bonding agent, make thickener, press LiCoO with polyvinyl alcohol with acrylonitrile-butadiene latex
2: conductive agent: gelatin: acrylonitrile-butadiene latex: polyvinyl alcohol=100:2:1:6:0.1 batching.
At first the 10g gelatin is obtained gelatin solution with the 450ml dissolved in purified water, then 1g polyvinyl alcohol (molecular weight is 450,000) is dissolved in the 220ml pure water fully, with the 450ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, add the poly-vinyl alcohol solution and the 60 gram acrylonitrile-butadiene latex that prepare, stirred 3 hours again, then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment four, make auxiliary bonding agent, make thickener, press LiCoO with Sodium Polyacrylate with PTFE latex
2: conductive agent: gelatin: PTFE latex: Sodium Polyacrylate=100:2:1:0.5; 3 batchings.
At first the 10g gelatin is obtained gelatin solution with the 300ml dissolved in purified water, then 30g Sodium Polyacrylate (molecular weight is 50,000) is dissolved in the 410ml pure water fully, with the 300ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, add the sodium polyacrylate solution and the 5 gram acrylonitrile-butadiene latex that prepare, stirred 3 hours again, then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment five, make auxiliary bonding agent, make thickener, press LiCoO with polyacrylamide with SBR
2: conductive agent: gelatin: SBR: polyacrylamide=100:2:1:1.5:0.5 batching.
At first the 10g gelatin is obtained gelatin solution with the 350ml dissolved in purified water, then 5g polyacrylamide (molecular weight is 250,000) is dissolved in the 360ml pure water fully, with the 350ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, the polyacrylamide solution that adds 15 gram SBR and prepare stirred 3 hours again, and then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment six, each proportioning and preparation method and embodiment five are basic identical, and just to change molecular weight into be 250,000 polyacrylic acid alcohol ester to thickener.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment seven, make auxiliary bonding agent, make thickener, press LiCoO with PEO with SBR
2: conductive agent: gelatin: SBR:PEO=100:0.5:1:3:0.5 batching.
At first the 5g gelatin is obtained gelatin solution with the 300ml dissolved in purified water, then 5g PEO (molecular weight is 250,000) is dissolved in the 420ml pure water fully, with the 300ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, the PEO solution that adds 30 gram SBR and prepare stirred 3 hours again, and then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment eight, make auxiliary bonding agent, make thickener, press LiCoO with Sodium Polyacrylate with SBR
2: conductive agent: gelatin: SBR: Sodium Polyacrylate=100:2:4:1:0.5 batching.
At first the 40g gelatin is obtained gelatin solution with the 350ml dissolved in purified water, then 5g Sodium Polyacrylate (molecular weight is 450,000) is dissolved in the 360ml pure water fully, with the 350ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, the sodium polyacrylate solution that adds 10 gram SBR and prepare stirred 3 hours again, and then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment nine, make auxiliary bonding agent, make thickener, press LiCoO with PEO with SBR
2: conductive agent: gelatin: SBR:PEO=100:2:3:2:0.5 batching.
At first the 30g gelatin is obtained gelatin solution with the 350ml dissolved in purified water, then 5g PEO (molecular weight is 250,000) is dissolved in the 350ml pure water fully, with the 350ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, the PEO solution that adds 20 gram SBR and prepare stirred 3 hours again, and then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment ten, make auxiliary bonding agent, make thickener, press LiCoO with PEO with SBR
2: conductive agent: gelatin: SBR:PEO=100:2:0.5:1:4.5 batching.
At first the 5g gelatin is obtained gelatin solution with the 350ml dissolved in purified water, then 45g PEO (molecular weight is 250,000) is dissolved in the 350ml pure water fully, with the 350ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, the PEO solution that adds 10 gram SBR and prepare stirred 3 hours again, and then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment 11, make auxiliary bonding agent, make thickener, press LiCoO with PEO with SBR
2: conductive agent: gelatin: SBR:PEO=100:2:1.5:1.5:0.5 batching.
At first the 15g gelatin is obtained gelatin solution with the 350ml dissolved in purified water, then the poly-PEO (molecular weight is 250,000) of 5g is dissolved in the 360ml pure water fully, with the 350ml gelatin solution for preparing and the LiCoO of 1000g drying
2Positive electrode powder (manufacturing of company of CITIC Guoan) is poured in the small-sized eggbeater, stir half an hour with per minute 2000 rotating speeds, then in above-mentioned mixture, divide 3 batches to add conductive agent Super P 20g, continued high-speed stirred 2 hours, after treating slurry cardinal principle mixing, the sodium polyacrylate solution that adds 15 gram SBR and prepare stirred 3 hours again, and then the slurry preparation is finished.In vacuum drying chamber, vacuumized 1 hour, and behind mistake 150 mesh sieves, just can be coated with then.It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment 12, each proportioning and preparation method change LiNiO into embodiment nine identical just positive electrode powder substantially
2It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Embodiment 13, each proportioning and preparation method change LiMn into embodiment nine identical just positive electrode powder substantially
2O
4It is basic identical with the battery performance of oil phase coating usually to contain the lithium ion battery of the positive plate that uses the said method manufacturing.
Below the performance of the lithium ion battery of the positive plate production of making according to the inventive method is adopted in explanation.
(1) manufacturing of positive plate
Water-based slurry with embodiment 11 preparations is coated with 4 meters long coating machines.The temperature of three dry drying tunnels is set to 100,120 and 100 ℃ respectively before, during and after the coating machine.Used collector aluminum foil thickness is 20 μ m, and wide 280mm, single face aluminium foil coating thickness are 130 μ m, and the double spread THICKNESS CONTROL is at 250 μ m.Slurry with the above-mentioned condition coating embodiment of the invention one-13 all can be processed smoothly, and can get surface density as the slurry with embodiment one is 425g/m
2Positive plate, and pole piece is softer and not easy to break.In contrast, if not according to method of the present invention, only make bonding agent with gelatin, when then being coated on single face with above-mentioned coating machine, it is serious that pole piece " falls material ", is grizzled shape; Be coated with when two-sided, situation is good slightly, yet pole piece is harder, easy aliquation during doubling.
(2) manufacturing of negative plate
The negative plate manufacturing is undertaken by liquid electrolyte lithium ion battery negative plate production technology.Negative material is selected Changsha Xing Cheng graphite for use, bonding agent use bonding agent sodium carboxymethylcellulose (CMC) and SBR latex.During slurrying, CMC with 2 parts of weight is dissolved in 100 parts of water earlier, then, under agitation add 5 parts of weight SBR latex, finish, add 92 parts of graphite powders again, and high degree of agitation is 4 hours continuously, can get cathode size, then with above-mentioned 4 meters long small-sized coating machines with the cathode size double spread on the thick Copper Foil of 12 μ m, promptly obtain negative plate after doing.
(3) manufacturing of square " 053048S " battery
Above-mentioned positive and negative plate and diaphragm paper (Celgard 2300) are cut according to model " 053048S " size that battery requires, then, again according to the usual technology of battery manufacturing, spot welding lug, baking sheet, coiling, dress shell, Laser Welding cover plate, drying and fluid injection successively, gained battery referable preliminary filling and changing into.
(4) battery testing
The semi-finished product battery that drying is good injects the organic electrolyte of 2.4g, place after 2 hours, test with certain system of discharging and recharging, the system of discharging and recharging is: the 1st step was with 0.05CmA electric current constant current charge 60 minutes, the 2nd step was with 0.1CmA electric current constant current charge 50 minutes, the 3rd step then with 0.5CmA electric current constant current charge till the 4.2V, the 4th step was then used constant voltage 4.2V instead, and to charge to electric current be 30mA, after leaving standstill 5 minutes, the 5th the step again with 0.5CmA electric current constant-current discharge to cut-ff voltage 3.0V, after leaving standstill 5 minutes, the 6th step was with 1CmA electric current constant-current constant-voltage charging, and the 7th step then used the 1CmA current discharge to cut-ff voltage 2.75V, electricity is so just finished preliminary filling and is changed into step, at last, with battery seal, get final product to such an extent that model is " 053048S " finished steel housing battery.
Then, the battery of finishing preliminary filling and change into is carried out loop test by following system, its system is: the 1st step, be 4.2V with 1CmA electric current constant current charge to voltage earlier, the 2nd step was 30mA with 4.2V voltage constant voltage charge to electric current, left standstill 5 minutes, the 3rd step, with 1CmA electric current constant-current discharge to cut-ff voltage 2.75V, the number of times that needs with the circulation of such system.
Comparative Examples one
Adopt the LiCoO of CITIC Guoan with the commercialization lithium rechargeable battery
2For the N-methyl pyrrolidone of positive electrode, Kynoar (PVDF) is that bonding agent makes positive plate, positive pole consists of: LiCoO
21000 grams, Super P 28 grams, PVDF 30 grams, NMP 400 grams.Make negative plate and make 053048S box hat battery by embodiment 11, method of testing is the same.
Test shows, adopt the battery of the positive plate of the inventive method manufacturing to compare with the battery of common oil phase coating, performance basic identical (seeing accompanying drawing 3), test through 100 cycle charge and discharge cycles, the discharge capacitance of the battery of the positive plate of employing the inventive method manufacturing can reach 92%, reaches battery quality standard (seeing accompanying drawing 1 and accompanying drawing 2).
Must be pointed out, above-mentioned conductive agent bonding agent except adopting gelatin, also can adopt the class gelatin mass, substitutes such as algin, shitosan (chitin), poly-maltotriose for example are as long as it is just passable to be applicable to that the water coating can stick to conductive agent positive electrode active materials powder surface.
Claims (19)
1, a kind of based lithium-ion battery positive plate manufacture method, comprise water pulp preparation operation, comprise the step that raw material mixes in this operation, promptly, to comprise the positive electrode active materials powder, conductive agent, the raw material of conductive agent bonding agent is uniformly mixed into the paste slurry, described conductive agent bonding agent is used for conductive agent is evenly sticked to positive electrode active materials powder surface, it is characterized in that: also add in the step that described raw material mixes and be used to adjust the thickener that mixes the gained slurry viscosity and be used to improve the adhesive property between positive electrode and the collector and improve the auxiliary bonding agent of pole piece flexibility, described thickener is the mixture of water-soluble high-molecular compound or water-soluble high-molecular compound.
2, based lithium-ion battery positive plate manufacture method according to claim 1 is characterized in that: described conductive agent bonding agent is a gelatin.
3, based lithium-ion battery positive plate manufacture method according to claim 2, it is characterized in that: described water-soluble high-molecular compound is selected from: polyvinyl alcohol, polyethylene glycol oxide, polyacrylamide, Sodium Polyacrylate, polyacrylic acid alcohol ester, polyvinylpyrrolidone.
4, based lithium-ion battery positive plate manufacture method according to claim 3, it is characterized in that: described water-soluble high-molecular compound is selected from: polyvinyl alcohol, polyethylene glycol oxide, Sodium Polyacrylate, polyacrylic acid alcohol ester.
5, based lithium-ion battery positive plate manufacture method according to claim 4, it is characterized in that: the molecular weight of each polymer is respectively: polyvinyl alcohol 50000～450000, polyethylene glycol oxide 50000～450000, Sodium Polyacrylate 50000～250000, polyacrylic acid alcohol ester 50000～150000.
6, according to any described based lithium-ion battery positive plate manufacture method of claim 1～5, it is characterized in that: described auxiliary bonding agent is following material or their mixture: butadiene-styrene rubber, acrylonitrile-butadiene latex, polytetrafluoroethylene latex.
7, based lithium-ion battery positive plate manufacture method according to claim 6 is characterized in that: described auxiliary bonding agent is a butadiene-styrene rubber.
8, according to any described based lithium-ion battery positive plate manufacture method of claim 2～5, it is characterized in that: described gelatin consumption is 0.5～4.0% of a positive electrode active materials weight.9, according to any described based lithium-ion battery positive plate manufacture method of claim 1～5, it is characterized in that: the consumption of described thickener is 0.1～3.0% of a positive electrode active materials weight.
10, based lithium-ion battery positive plate manufacture method according to claim 6 is characterized in that: the consumption of described thickener is 0.1～3.0% of a positive electrode active materials weight.
11, according to any described based lithium-ion battery positive plate manufacture method of claim 1～5, it is characterized in that: the consumption of described auxiliary bonding agent is 0.5～6.0% of a positive electrode active materials weight.
12, based lithium-ion battery positive plate manufacture method according to claim 6 is characterized in that: the consumption of described auxiliary bonding agent is 0.5～6.0% of a positive electrode active materials weight.
13, based lithium-ion battery positive plate manufacture method according to claim 8 is characterized in that: described gelatin consumption is 1.0～3.0% of a positive electrode active materials weight.
14, based lithium-ion battery positive plate manufacture method according to claim 9 is characterized in that: the consumption of described thickener is 0.5～2.0% of a positive electrode active materials weight.
15, based lithium-ion battery positive plate manufacture method according to claim 10 is characterized in that: the consumption of described thickener is 0.5～2.0% of a positive electrode active materials weight.
16, based lithium-ion battery positive plate manufacture method according to claim 11 is characterized in that: the consumption of described auxiliary bonding agent is 1.0～4.5% of a positive electrode active materials weight.
17, based lithium-ion battery positive plate manufacture method according to claim 12 is characterized in that: the consumption of described auxiliary bonding agent is 1.0～4.5% of a positive electrode active materials weight.
18, according to any described based lithium-ion battery positive plate manufacture method of claim 1～5, it is characterized in that: described positive electrode active materials comprises and is selected from LiCoO
2, LiNiO
2Or LiMnO
2Lithium compound.19, based lithium-ion battery positive plate manufacture method according to claim 6 is characterized in that: described positive electrode active materials comprises and is selected from LiCoO
2, LiNiO
2Or LiMnO
2Lithium compound.
20, a kind of positive plate of the lithium ion battery of making according to the described method of above-mentioned any one claim.
21, a kind of lithium ion battery with the described positive plate of claim 20.
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| CN103137334B (en) * | 2011-12-01 | 2016-06-08 | 上海奥威科技开发有限公司 | For the making method of electrode slice and the ultracapacitor of ultracapacitor |
| JP6354135B2 (en) * | 2013-02-12 | 2018-07-11 | 株式会社ジェイテクト | Electric storage material manufacturing apparatus and manufacturing method |
| FR3048821B1 (en) * | 2016-03-08 | 2021-12-17 | Commissariat Energie Atomique | INK INCLUDING A MIXTURE OF POLYACRYLIC ACIDS FOR THE REALIZATION OF A LITHIUM-ION BATTERY ELECTRODE, AND ELECTRODE OBTAINED WITH SUCH AN INK |
| CN106099114B (en) * | 2016-08-19 | 2018-12-18 | 洛阳力容新能源科技有限公司 | A kind of lithium ion battery compound binding agent, lithium ion battery anode glue size and lithium ion battery |
| CN106898771B (en) * | 2017-04-27 | 2020-02-21 | 柳州豪祥特科技有限公司 | Lithium-iron disulfide battery anode material |
| CN108281660A (en) * | 2018-01-24 | 2018-07-13 | 广州鹏辉能源科技股份有限公司 | Anode material for lithium-ion batteries, based lithium-ion battery positive plate and preparation method thereof and lithium ion battery |
| CN112175134B (en) * | 2020-09-30 | 2023-03-24 | 珠海冠宇电池股份有限公司 | Binder and lithium ion battery containing same |
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Effective date of registration: 20160519 Address after: An Zhen Zhongmu County 450000 Henan city of Zhengzhou Province Liu Zheng Qiao Village Patentee after: ZHENGZHOU BIKE BATTERY CO., LTD. Address before: Kwai Chung street Beek Industrial Park in Longgang District of Shenzhen City, Guangdong province 518119 Patentee before: Shenzhen Bak Battery Co., Ltd. |
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