CN103094556A - Method for preparing positive electrode slurry of lithium ion battery - Google Patents
Method for preparing positive electrode slurry of lithium ion battery Download PDFInfo
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- CN103094556A CN103094556A CN2013100404886A CN201310040488A CN103094556A CN 103094556 A CN103094556 A CN 103094556A CN 2013100404886 A CN2013100404886 A CN 2013100404886A CN 201310040488 A CN201310040488 A CN 201310040488A CN 103094556 A CN103094556 A CN 103094556A
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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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Abstract
The invention discloses a method for preparing anode slurry of a lithium ion battery. The method comprises the following steps of: mixing and stirring 50 parts of N-methyl pyrrolidone and 3 parts of polyvinylidene fluoride for 120 minutes, adding 4 parts of conductive agent and stirring for 120 minutes, adding 93 parts of positive electrode materials, adding 50 parts of N-methyl pyrrolidone, stirring for 270 minutes, and filtering the slurry which is completely stirred through a 150-mesh filtering net. By adoption of the technical scheme, the method has the advantages that 1. the positive electrode material is a mixed material of lithium manganate and nickel cobalt lithium manganate; 2. the N-methyl pyrrolidone and 3 percent of polyvinylidene fluoride are mixed to prepare colloid; and 3. 4 percent of conductive agent is added for stirring, 93 percent of positive electrode material is added twice and uniformly mixing. The proportioning formula of the positive electrode material is adjusted, and the homogenizing process is improved, so that the slurry is fully dispersed, and compared with the conventional lithium manganate battery, the prepared lithium manganate battery has the obvious advantages that the capacity attenuation rate is reduced, the cycle lift is prolonged, and the cycle performance of the battery is improved.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery anode glue size.
Background technology
At present, LiMn2O4 has the advantages such as aboundresources, high voltage, low cost, to have wide market prospects in fields such as the energy, traffic, environmental protection, communication and oceans, but because the cycle performance of lithium manganate material is poor high with the capacity attenuation rate, restricted lithium manganate battery part development in the industry.
Summary of the invention
A kind of positive electrode that technical problem to be solved by this invention is to provide a kind of suitable suitability for industrialized production, have extended cycle life is the preparation method that ternary is mixed the lithium ion battery anode glue size of LiMn2O4.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: the preparation method of lithium ion battery anode glue size, after 1-METHYLPYRROLIDONE and 3 weight portion Kynoar mix and blend 120min with 50 weight portions, add 4 weight portion conductive agents to stir 120min, add 93 weight portion positive electrodes, add simultaneously the 1-METHYLPYRROLIDONE of 50 weight portions again, stir 270min, the slurry that stirs after completing is crossed 150 mesh filter screens filtrations.
As preferably, the ambient humidity in operating process≤45%, speed of agitator 1800-2200r/min, the vacuum degree of agitator tank≤-0.09MPa; Slurry is controlled temperature at 20 ~ 45 ℃.
As preferably, described positive electrode is the mixture of LiMn2O4 and ternary material, and the mass ratio of LiMn2O4 and ternary material is 2:3.
As preferably, described ternary material is nickle cobalt lithium manganate.
The present invention is owing to having adopted technique scheme, and its advantage is: 1. positive electrode is that LiMn2O4 and nickle cobalt lithium manganate composite material 2. first are mixed and made into colloid with 1-METHYLPYRROLIDONE and 3% Kynoar; 3. add 4% conductive agent after and stir, then put at twice 93% positive electrode and mix.The present invention is by adjusting positive electrode ratio formula and improving the homogenate process, slurry is fully disperseed, and the lithium manganate battery of its preparation compares with existing lithium manganate battery and has the remarkable advantage that the capacity attenuation rate reduces, has extended cycle life, and improved the cycle performance of battery.
Embodiment
The present invention is fully disperseed slurry by improving the homogenate process; By adjusting positive electrode ratio formula, the lithium ion battery of its preparation is compared with existing lithium manganate battery has the remarkable advantage that the capacity attenuation rate reduces, has extended cycle life.
Embodiment one
(1) anodal homogenate after 1-METHYLPYRROLIDONE and 3% Kynoar mix and blend 120min, adds 4% conductive agent to stir 120min, and the positive electrode 93% adds with 1:1 at twice, adds simultaneously 1-METHYLPYRROLIDONE, stirs 270min.Described positive electrode is the mixture of LiMn2O4 and ternary material, and mass ratio is 2:3, and the total amount of 1-METHYLPYRROLIDONE is 40～50% of slurry total amount.Ambient humidity in described operating process is not more than 45%, speed of agitator 1800-2200r/min, and vacuum degree is not higher than-0.09MPa; It is 20 ~ 45 ℃ that slurry is controlled temperature, and when higher (slurry heat up) is with alcohol wipe homogenate pot or add cooling water or the reduction rotating speed in case of necessity.Discharging viscosity 6500-8500MPas, solid content 50～60%.Slurry after stirring is completed is crossed 150 mesh filter screens and is filtered, and obtains anode sizing agent.
(2) negative pole homogenate, the negative electrode active material with 94.5%, 1～1.5% conductive black, 1～2% sodium carboxymethylcellulose, deionized water stir 300min, add 2.5～3.5% butadiene-styrene rubber binding agents, stir 60min.The total amount of described conductive black, sodium carboxymethylcellulose and butadiene-styrene rubber accounts for 5.5% of negative material total amount, and the ambient humidity in operating process is not more than 45%, speed of agitator 1800-2200r/min, and vacuum degree is not higher than-0.09MPa; It is 20 ~ 40 ℃ that slurry is controlled temperature, discharging viscosity 3000-4000MPas, solid content 40～50%.Slurry after stirring is completed is crossed 100 mesh filter screens and is filtered, and obtains cathode size.
(3) with anode sizing agent 100～140 ℃ of temperature, speed 4～6m/min is coated on the aluminium foil of 18～22 μ m, single face surface density 210 ± 3g/m
2, two-sided surface density 420 ± 5g/m
260～100 ℃ of temperature, speed 5～7m/min is coated on the Copper Foil of 7～11 μ m, single face surface density 103 ± 3g/m with cathode size
2, two-sided surface density 206 ± 5g/m
2
(4) the both positive and negative polarity pole piece is suppressed by roll squeezer, anodal thickness is 160 ± 2 μ m, and negative pole thickness is 154 ± 2 μ m.
(5) the every 200mm of positive plate cut a sheet of, every a sheet of positive plate that cuts out again long 115mm, wide 64mm; The every 204mm of negative plate cuts a sheet of, every a sheet of negative plate that cuts out again long 117mm, wide 65mm.
(6) the both positive and negative polarity pole piece that cuts is put into respectively 80 ℃ of baking ovens, oven dry 36h.
(7) use laminating machine, make anode pole piece, barrier film, cathode pole piece build up in order battery core, several 29 of anode pole piece, 30 of cathode pole pieces.
(8) with the battery core soldering polar ear of folding and the housing of packing into, inject electrolyte in housing, seal housing with heat sealing machine.
(9) after battery cell is shelved 36h, first with 0.05C current charges 60min, then with 0.1C current charges 60min, stop with 0.2C current charges 150min at last, 55 ℃ of high temperature of described cell are shelved 10h.
(10) battery cell normal temperature cooling after, first with the 0.2C constant-current constant-voltage charging to 4.2V, cut-off current is 0.02C, afterwards with the 0.2C constant-current discharge to 3.0V, again with first with the 0.5C constant-current constant-voltage charging to 4.2V, cut-off current is 0.02C, with the 0.5C constant-current discharge to 3.0V.
Embodiment two
(1) anodal homogenate after 1-METHYLPYRROLIDONE and 3% Kynoar mix and blend 120min, adds 4% conductive agent to stir 120min, and the positive electrode 93% adds with 1:1 at twice, adds simultaneously 1-METHYLPYRROLIDONE, stirs 270min.Described positive electrode is the mixture of LiMn2O4 and ternary material, and mass ratio is 1:1, and the total amount of 1-METHYLPYRROLIDONE is 40～50% of slurry total amount.Ambient humidity in described operating process is not more than 45%, speed of agitator 1800-2200r/min, and vacuum degree is not higher than-0.09MPa; It is 20 ~ 45 ℃ that slurry is controlled temperature, and when higher (slurry heat up) is with alcohol wipe homogenate pot or add cooling water or the reduction rotating speed in case of necessity.Discharging viscosity 6500-8500MPas, solid content 50～60%.Slurry after stirring is completed is crossed 150 mesh filter screens and is filtered, and obtains anode sizing agent.
(2) negative pole homogenate, the negative electrode active material with 94.5%, 1～1.5% conductive black, 1～2% sodium carboxymethylcellulose, deionized water stir 300min, add 2.5～3.5% butadiene-styrene rubber binding agents, stir 60min.The total amount of described conductive black, sodium carboxymethylcellulose and butadiene-styrene rubber accounts for 5.5% of negative material total amount, and the ambient humidity in operating process is not more than 45%, speed of agitator 1800-2200r/min, and vacuum degree is not higher than-0.09MPa; It is 20 ~ 40 ℃ that slurry is controlled temperature, discharging viscosity 3000-4000MPas, solid content 40～50%.Slurry after stirring is completed is crossed 100 mesh filter screens and is filtered, and obtains cathode size.
(3) with anode sizing agent 100～140 ℃ of temperature, speed 4～6m/min is coated on the aluminium foil of 18～22 μ m, single face surface density 193 ± 3g/m
2, two-sided surface density 385 ± 5g/m
260～100 ℃ of temperature, speed 5～7m/min is coated on the Copper Foil of 7～11 μ m, single face surface density 100 ± 3g/m with cathode size
2, two-sided surface density 200 ± 5g/m
2
(4) the both positive and negative polarity pole piece is suppressed by roll squeezer, anodal thickness is 142 ± 2 μ m, and negative pole thickness is 150 ± 2 μ m.
(5) the every 200mm of positive plate cut a sheet of, every a sheet of positive plate that cuts out again long 115mm, wide 64mm; The every 204mm of negative plate cuts a sheet of, every a sheet of negative plate that cuts out again long 117mm, wide 65mm.
(6) the both positive and negative polarity pole piece that cuts is put into respectively 80 ℃ of baking ovens, oven dry 36h.
(7) use laminating machine, make anode pole piece, barrier film, cathode pole piece build up in order battery core, several 31 of anode pole piece, 32 of cathode pole pieces.
(8) with the battery core soldering polar ear of folding and the housing of packing into, inject electrolyte in housing, seal housing with heat sealing machine.
(9) after battery cell is shelved 36h, first with 0.05C current charges 60min, then with 0.1C current charges 60min, stop with 0.2C current charges 150min at last, 55 ℃ of high temperature of described cell are shelved 10h.
(10) battery cell normal temperature cooling after, first with the 0.2C constant-current constant-voltage charging to 4.2V, cut-off current is 0.02C, afterwards with the 0.2C constant-current discharge to 3.0V, again with first with the 0.5C constant-current constant-voltage charging to 4.2V, cut-off current is 0.02C, with the 0.5C constant-current discharge to 3.0V.
Comparative Examples:
(1) anodal homogenate after 1-METHYLPYRROLIDONE and 3% Kynoar mix and blend 120min, adds 4% conductive agent to stir 120min, and 93% manganate cathode material for lithium is added with 1:1 at twice, adds simultaneously 1-METHYLPYRROLIDONE, stirs 270min.The total amount of described 1-METHYLPYRROLIDONE is that the ambient humidity in 40～50% operating process of slurry total amount is not more than 45%, speed of agitator 1800-2200r/min, and vacuum degree is not higher than-0.09MPa; It is 20 ~ 45 ℃ that slurry is controlled temperature, and when higher (slurry heat up) is with alcohol wipe homogenate pot or add cooling water or the reduction rotating speed in case of necessity.Discharging viscosity 6500-8500MPas, solid content 50～60%.Slurry after stirring is completed is crossed 150 mesh filter screens and is filtered, and obtains anode sizing agent.
(2) negative pole homogenate, the negative electrode active material with 94.5%, 1～1.5% conductive black, 1～2% sodium carboxymethylcellulose, deionized water stir 300min, add 2.5～3.5% butadiene-styrene rubber binding agents, stir 60min.The total amount of described conductive black, sodium carboxymethylcellulose and butadiene-styrene rubber accounts for 5.5% of negative material total amount, and the ambient humidity in operating process is not more than 45%, speed of agitator 1800-2200r/min, and vacuum degree is not higher than-0.09MPa; It is 20 ~ 40 ℃ that slurry is controlled temperature, discharging viscosity 3000-4000MPas, solid content 40～50%.Slurry after stirring is completed is crossed 100 mesh filter screens and is filtered, and obtains cathode size.
(3) with anode sizing agent 100～140 ℃ of temperature, speed 4～6m/min is coated on the aluminium foil of 18～22 μ m, single face surface density 175 ± 3g/m
2, two-sided surface density 350 ± 5g/m
260～100 ℃ of temperature, speed 5～7m/min is coated on the Copper Foil of 7～11 μ m, single face surface density 78 ± 3g/m with cathode size
2, two-sided surface density 156 ± 5g/m
2
(4) the both positive and negative polarity pole piece is suppressed by roll squeezer, anodal thickness is 140 ± 2 μ m, and negative pole thickness is 125 ± 2 μ m.
(5) the every 200mm of positive plate cut a sheet of, every a sheet of positive plate that cuts out again long 115mm, wide 64mm; The every 204mm of negative plate cuts a sheet of, every a sheet of negative plate that cuts out again long 117mm, wide 65mm.
(6) the both positive and negative polarity pole piece that cuts is put into respectively 80 ℃ of baking ovens, oven dry 36h.
(7) use laminating machine, make anode pole piece, barrier film, cathode pole piece build up in order battery core, several 22 of anode pole piece, 23 of cathode pole pieces.
(8) with the battery core soldering polar ear of folding and the housing of packing into, inject electrolyte in housing, seal housing with heat sealing machine.
(9) after battery cell is shelved 36h, first with 0.05C current charges 60min, then with 0.1C current charges 60min, stop with 0.2C current charges 150min at last, 55 ℃ of high temperature of described cell are shelved 10h.
(10) battery cell normal temperature cooling after, first with the 0.2C constant-current constant-voltage charging to 4.2V, cut-off current is 0.02C, afterwards with the 0.2C constant-current discharge to 3.0V, again with first with the 0.5C constant-current constant-voltage charging to 4.2V, cut-off current is 0.02C, with the 0.5C constant-current discharge to 3.0V.
Under 25 ℃ of test conditions, when capability retention ended 80%, the cycle-index of embodiment one was 2086 times, and the cycle-index of embodiment two is 1779 times, and the cycle-index of Comparative Examples 1 is more than 1300 time.Embodiment one, embodiment two compare cycle-index and improve respectively 58%, 35% with Comparative Examples.
Claims (4)
1. the preparation method of lithium ion battery anode glue size, it is characterized in that: after 1-METHYLPYRROLIDONE and 3 weight portion Kynoar mix and blend 120min with 50 weight portions, add 4 weight portion conductive agents to stir 120min, add 93 weight portion positive electrodes, add again simultaneously the 1-METHYLPYRROLIDONE of 50 weight portions, stir 270min, the slurry that stirs after completing is crossed 150 mesh filter screens filtrations.
2. the preparation method of lithium ion battery anode glue size according to claim 1 is characterized in that: the ambient humidity in operating process≤45%, and speed of agitator 1800-2200r/min, the vacuum degree of agitator tank≤-0.09MPa; Slurry is controlled temperature at 20 ~ 45 ℃.
3. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterized in that: described positive electrode is the mixture of LiMn2O4 and ternary material, the mass ratio of LiMn2O4 and ternary material is 2:3.
4. the preparation method of lithium ion battery anode glue size according to claim 3, it is characterized in that: described ternary material is nickle cobalt lithium manganate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682246A (en) * | 2013-12-13 | 2014-03-26 | 武汉昊诚能源科技有限公司 | High load Li-Mn battery and preparation method thereof |
| CN103811801A (en) * | 2014-03-17 | 2014-05-21 | 山东润峰集团新能源科技有限公司 | Preparation method of liquid flexible packaged low-temperature lithium ion battery |
| CN104538640A (en) * | 2015-01-04 | 2015-04-22 | 合肥国轩高科动力能源股份公司 | Lithium ion battery anode slurry and preparation method thereof |
| CN105185952A (en) * | 2015-08-26 | 2015-12-23 | 浙江超威创元实业有限公司 | Homogenizing method for lithium-ion battery cathode |
| CN105336943A (en) * | 2015-11-24 | 2016-02-17 | 四川省有色冶金研究院有限公司 | Lithium battery formed on basis of lithium nickel manganese oxide and lithium titanate and preparation method of lithium battery |
| CN105355922A (en) * | 2015-11-03 | 2016-02-24 | 百顺松涛（天津）动力电池科技发展有限公司 | Polyindole crosslinked polyvinylidene fluoride binder and lithium ion battery applying the same |
| CN105355903A (en) * | 2015-11-24 | 2016-02-24 | 四川省有色冶金研究院有限公司 | Nickel lithium manganate-based positive electrode material of lithium ion battery and preparation method thereof |
| CN105826595A (en) * | 2015-01-06 | 2016-08-03 | 深圳市比克电池有限公司 | Application of alpha-MoO3-modified graphene in lithium ion battery and lithium ion battery thereof |
| CN110911638A (en) * | 2019-10-15 | 2020-03-24 | 东莞赣锋电子有限公司 | Lithium ion battery with high-voltage ternary material doped with lithium manganate and preparation method |
| CN111697207A (en) * | 2019-03-14 | 2020-09-22 | 深圳格林德能源集团有限公司 | High-nickel ternary positive electrode slurry for lithium battery and preparation method of high-nickel ternary positive electrode slurry |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105826595A (en) * | 2015-01-06 | 2016-08-03 | 深圳市比克电池有限公司 | Application of alpha-MoO3-modified graphene in lithium ion battery and lithium ion battery thereof |
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| CN105355922A (en) * | 2015-11-03 | 2016-02-24 | 百顺松涛（天津）动力电池科技发展有限公司 | Polyindole crosslinked polyvinylidene fluoride binder and lithium ion battery applying the same |
| CN105336943A (en) * | 2015-11-24 | 2016-02-17 | 四川省有色冶金研究院有限公司 | Lithium battery formed on basis of lithium nickel manganese oxide and lithium titanate and preparation method of lithium battery |
| CN105355903A (en) * | 2015-11-24 | 2016-02-24 | 四川省有色冶金研究院有限公司 | Nickel lithium manganate-based positive electrode material of lithium ion battery and preparation method thereof |
| CN111697207A (en) * | 2019-03-14 | 2020-09-22 | 深圳格林德能源集团有限公司 | High-nickel ternary positive electrode slurry for lithium battery and preparation method of high-nickel ternary positive electrode slurry |
| CN110911638A (en) * | 2019-10-15 | 2020-03-24 | 东莞赣锋电子有限公司 | Lithium ion battery with high-voltage ternary material doped with lithium manganate and preparation method |
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Application publication date: 20130508 |