CN101136497B - Method for improving capacitance of lithium secondary battery - Google Patents
Method for improving capacitance of lithium secondary battery Download PDFInfo
- Publication number
- CN101136497B CN101136497B CN2006100623559A CN200610062355A CN101136497B CN 101136497 B CN101136497 B CN 101136497B CN 2006100623559 A CN2006100623559 A CN 2006100623559A CN 200610062355 A CN200610062355 A CN 200610062355A CN 101136497 B CN101136497 B CN 101136497B
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- China
- Prior art keywords
- solvent
- active material
- positive active
- secondary battery
- lithium secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 29
- 229910052744 lithium Inorganic materials 0.000 title claims description 29
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000007774 positive electrode material Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims description 40
- 239000007767 bonding agent Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 230000004087 circulation Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009193 crawling Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
This invention discloses a method for increasing capacity of Li-secondary batteries including: mixing a solvent, adhesive, a positive active material and a conductive agent to prepare positive slurry in the following three steps: 1, putting part of the solvent into the adhesive and mixing them fully to dissolve them completely and then adding the conductive agent and mixing them fully, 2, puttingthe rest solvent into a positive active material to mix them fully and the positive active material is wet uniformly, 3, fully mixing the products got from step 1 and 2 fully, which increases dispersion degree of the conductive agent in the positive active material.
Description
Technical field
The present invention relates to lithium battery and make the field, be specifically related to a kind of method that improves capacitance of lithium secondary battery.
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,, also the lighting of the driving power of electronic equipment was had higher requirement, and promptly required lithium ion battery in littler spatial dimension, to store higher energy along with the lighting of mancarried electronic aid.In order to adapt to this trend, the various countries scientist is doing unremitting effort.Improving the capacity of lithium ion battery fermentation, generally be divided into two research directions: be the charge/discharge capacity that improves active material in the lithium ion battery on the one hand, this respect mainly is to find out the cobalt acid lithium that a kind of new active material substitutes present extensive use by research; Mainly be the capacity that improves battery by improvement on the other hand to the lithium ion battery manufacture craft.The lithium battery anode mixing procedure is generally and earlier solvent is dissolved bonding agent fully at present, it is added in positive electrode and the conductive agent stir again.But this mixing procedure can not well mix positive electrode and conductive agent, and the battery capacity that causes making is brought into play not high.
Summary of the invention
Purpose of the present invention is exactly at prior art problems, and a kind of method that can improve the performance of cathode plate for lithium secondary battery capacity is provided.
For achieving the above object, the present invention has adopted following technical scheme:
The invention discloses a kind of method that improves capacitance of lithium secondary battery, described method comprises that the step that solvent, bonding agent, positive active material and conductive agent are mixed prepares anode sizing agent, the step of described mixing comprises blend step I, blend step II and blend step III respectively
Described blend step I is meant partial solvent is added in the bonding agent that stirring is dissolved bonding agent fully, adds conductive agent afterwards and fully mixes;
Described blend step II is meant remaining solvent is added in the positive active material, fully mixes making positive active material evenly wetting;
Described blend step III is meant that the product that blend step I, II are obtained respectively fully mixes together.
Described positive active material is a kind of in the modified material of the modified material of cobalt acid lithium, LiMn2O4, cobalt acid lithium and LiMn2O4.
Described conductive agent is Super P-type conduction agent.
Described bonding agent is a polyvinylidene fluoride.
Described solvent is the N-methyl pyrrolidone.
In the described method, the percentage by weight that the total consumption of solvent accounts for positive active material is 40%～55%; The percentage by weight that the bonding agent consumption accounts for positive active material is 1.8%～4.0%; The percentage by weight that the conductive agent consumption accounts for positive active material is 1%～3%.
Preferably, to account for the percentage by weight of positive active material be 2.1% to described conductive agent consumption.
Further, described blend step I is meant that specifically the solvent that will account for total amount 50%～70% earlier adds in the bonding agent, stirs and makes it dissolving, adds the solvent that accounts for total amount 10%～30% again, continues to stir bonding agent is dissolved cmpletely.
Among the described blend step III, fully mixing is that to instigate the viscosity of mixing disposed slurry be 3000～6000mpa.s.
Described method further comprises after blend step III: the slurry that obtains was vacuumized and stirs 0.2～1 hour, cross 150 mesh sieves then.
Because adopted above scheme, the beneficial effect that the present invention is possessed is:
The present invention is by in the batch mixing process of lithium ion battery anode glue size, employing is carried out particular combinations with different compositions, and fully mix earlier the last mixing method of mixed together more respectively, increased the decentralization of conductive agent in positive electrode active materials effectively, and the available capacity that makes positive active material fully obtains performance, thereby has effectively improved the whole volume performance of battery; In addition, reduced the consumption of conductive agent, increased content of active substance, bigger help has also been arranged improving battery capacity.Method of the present invention has on average improved more than 2.1% the lithium rechargeable battery initial discharge capacity, and circulation back discharge capacity has on average improved more than 2.5%.
Embodiment
Method of the present invention is in the batch mixing process of lithium ion battery anode glue size, and each composition is carried out specific combination, and mixed together again after mixing is respectively then effectively improved the discharge capacity of the lithium ion battery that the anode sizing agent that obtains prepares.
The used raw material of method of the present invention comprises solvent, bonding agent, positive active material and conductive agent.Batch mixing process of the present invention comprises three blend steps substantially: blend step I, blend step II and blend step III.
In blend step I, at first solvent is partly added in the bonding agent, stirring is dissolved bonding agent fully, fully mixes toward wherein adding conductive agent then;
In blend step II, remaining solvent is added in the positive active material, fully mix making positive active material evenly wetting;
In blend step III, the product that blend step I, II are obtained respectively fully mixes together.
The present invention converges in the used preferred Shanghai of conductive agent the SuperP type conductive agent that general industrial chemical Co., Ltd produces.
Used positive active material in the inventive method can be selected cobalt acid lithium, LiMn2O4 or their this areas such as modified material material commonly used for use, preferably uses cobalt acid lithium or its modified material.Modification generally has doping vario-property and coating modification, is meant the modification of any one mode wherein herein.
Solvent and bonding agent can be selected the common solvent and the bonding agent of preparation lithium ion battery anode glue size in this area for use, and the solvent that preferably uses is N-methyl pyrrolidone (NMP) in the present invention, and bonding agent is polyvinylidene fluoride (PVDF).
Because lithium battery is non-aqueous electrolyte battery, by reducing the influence that institute's band moisture causes battery performance in the raw material as far as possible, used positive active material and bonding agent are before use all through overbaking eliminating moisture among the present invention.
In the used material of the invention described above, the total consumption of solvent is generally 40%～55% of positive active material consumption.The consumption of bonding agent is generally 1.8%～4.0% of positive active material consumption.The conductive agent consumption is 1%～3% of a positive active material consumption, preferred 2.1%.Above-mentionedly all be weight percentage.Among the present invention, the selection of solvent load mainly is based on the viscosity of slurry to be considered, if solvent load too much (being higher than 55%) can make the slurry viscosity that obtains at last too small, influences subsequent technique; And if solvent load very little, then makes the slurry viscosity that obtains excessive, flowability is not good.The selection of bonding agent consumption mainly is based on the consideration of slurry cementability, and when the bonding agent consumption was lower than 1.8%, the slurry cementability that obtains at last was bad, and the pole piece of producing with this slurry falls material easily; And when the bonding agent consumption was higher than 4.0%, though the slurry cementability that obtains at last is fine, the bonding agent too high levels certainly will cause the content of positive active material to reduce, thereby influenced battery capacity.If the consumption of conductive agent is (＜1%) very little, can influence the conductivity of battery, make the internal resistance of cell very big, influence the performance of battery; And if conductive agent is too much (〉 3%), the content of positive active material is reduced, influence the capacity of battery.
In blend step I, more abundant for the dissolving that makes bonding agent, preferred usually employing gradation adds the method for solvent.Such as, can in bonding agent, add the solvent that accounts for solvent total amount 50%～70% earlier, stir after bonding agent being dissolved substantially in 1～3 hour and to add the solvent that accounts for solvent total amount 10%～30% again, continue to stir 1～4 hour, bonding agent was dissolved fully in preferred 2～3 hours.Toward wherein adding the conductive agent that accounts for positive active material percentage by weight 1%～3%, abundant then stirring makes and mixes afterwards.
When carrying out blend step I, can in another container or blender, carry out blend step II, be about to remaining solvent and add in the positive active material, fully mix about 0.5～1 hour, make positive active material evenly wetting.
At last, carry out blend step III, the product that is about to blend step I joins in the product of blend step II, stir they are fully mixed, and to make the slurry viscosity that obtains at last is 3000～6000mpa.s.The mixing time of this step needs 3～8 hours usually.If the viscosity of slurry is low excessively, when being lower than 3000mpa.s, slurry is too rare, in the time of can causing follow-up making lithium ion cell positive, and the very low technological requirement that do not reach of coating back pole piece surface density; If the viscosity of slurry is too high, during greater than 6000mpa.s, then slurry fluidity is too poor, causes crawling even, does not reach the coating requirement equally.
The lithium ion battery anode glue size that makes by above-mentioned batch mixing process was crossed discharging behind 150 mesh sieves then through further stirring and vacuumizing, and vacuumized and mixing time is generally 0.2～1 hour.
More than mixing time and speed in each step, be as the criterion to satisfy mixing fully of each composition, also take into account as far as possible simultaneously and shorten man-hour.
The above-mentioned lithium ion battery anode glue size that obtains can make the positive pole of lithium ion battery again through steps such as conventional coating, roll-in, sections.The positive pole that makes adopts conventional manufacture method and material can make corresponding lithium ion battery, and the initial discharge capacity of this battery and circulation back discharge capacity all are significantly improved.
Be that example specifies realization of the present invention now with the lithium ion battery of making the 423443A model.
Embodiment 1
(1) batch mixing
The PVDF that accurately is cooled to 50 ℃ after the weighing 20 gram bakings is in blender, take by weighing 300 gram NMP again and add blender with dissolving PVDF, start blender and make it dissolving, approximately 1 hour consuming time, in blender, add 100 gram NMP again, continue stirring PVDF is dissolved fully, add 20.0 gram Super P conductive agents then, stirred again 1 hour, and made it even mixing, stand-by.
Cobalt acid lithium 1000 grams that accurately are cooled to after the weighing baking below 50 ℃ place blender, add the NMP100 gram then, start blender stir about 1 hour, make it evenly wetting.Step mixes above adding again bonding agent and conductive agent, stir about 5 hours, measuring its viscosity is 4500mpa.s, vacuum stirring 20 minutes is crossed 150 mesh sieves, discharging then.
(2) coating
According to being used to technology the slurry for preparing above is coated on the collector aluminium foil uniformly, avoids occurring phenomenon appearance such as dew paper tinsel, accurately grasp and cover the material amount, making it surface density is about 44.5mg/cm2.
Each technology is with identical according to the manufacture craft of being used to lithium battery later on.The battery of making is carried out the test of chemical property, and recording its initial discharge capacity is 732.6ma.h, discharge and recharge 100 circulations after, its discharge capacity is 694.9ma.h, the capability retention of 100 circulations is 94.85%.
Comparative Examples 1
Because the raw-material charging sequence difference of each component when difference with the prior art part of the present invention is batch mixing, existing its difference of only describing: the PVDF20 gram after will toasting earlier places blender, adds 500 gram NMP again, stirs and makes it even mixing, and is stand-by.Just baking back 1000 gram cobalt acid lithiums and 20 gram Super P conductive agents are put into another blender again, and the bonding agent that adding prepares above mixes.Follow-up cell making process is finished in the discharging that vacuumizes and sieve evenly again.The battery of making is carried out the test of chemical property, and recording its initial discharge capacity is 702.6ma.h, discharge and recharge 100 circulations after, its discharge capacity is 654.8ma.h, the capability retention of 100 circulations is 93.2%.
Embodiment 2-6 and relevant Comparative Examples thereof and embodiment 1 and Comparative Examples 1 manufacture craft are basic identical, and variant part describes in detail in table 1.
Each embodiment of table 1 and Comparative Examples technological parameter and test result (positive electrode all is 1000 grams)
According to last table as can be known, for positive electrode of the same race and each raw-material proportioning, by the improvement to mixing procedure, discharge capacity of the cell is all than the height before improving.Method of the present invention has on average improved more than 2.1% the lithium rechargeable battery initial discharge capacity, and circulation back discharge capacity has on average improved more than 2.5%.Though mixing procedure than prior art complexity, can effectively improve the capacity of battery, this kind mixing procedure is worthy to be popularized.
Claims (10)
1. method that improves capacitance of lithium secondary battery, described method comprises that the step that solvent, bonding agent, positive active material and conductive agent are mixed prepares anode sizing agent, it is characterized in that: the step of described mixing comprises blend step I, blend step II and blend step III respectively
Described blend step I is meant partial solvent is added in the bonding agent that stirring is dissolved bonding agent fully, adds conductive agent afterwards and fully mixes;
Described blend step II is meant remaining solvent is added in the positive active material, fully mixes making positive active material evenly wetting;
Described blend step III is meant that the product that blend step I, II are obtained respectively fully mixes together.
2. a kind of method that improves capacitance of lithium secondary battery according to claim 1 is characterized in that: described positive active material is a kind of in the modified material of the modified material of cobalt acid lithium, LiMn2O4, cobalt acid lithium and LiMn2O4.
3. a kind of method that improves capacitance of lithium secondary battery according to claim 1 is characterized in that: described conductive agent is Super P-type conduction agent.
4. a kind of method that improves capacitance of lithium secondary battery according to claim 1 is characterized in that: described bonding agent is a polyvinylidene fluoride.
5. a kind of method that improves capacitance of lithium secondary battery according to claim 1 is characterized in that: described solvent is the N-methyl pyrrolidone.
6. according to any described a kind of method that improves capacitance of lithium secondary battery of claim 1～5, it is characterized in that: in the described method, the percentage by weight that the total consumption of solvent accounts for positive active material is 40%～55%; The percentage by weight that the bonding agent consumption accounts for positive active material is 1.8%～4.0%; The percentage by weight that the conductive agent consumption accounts for positive active material is 1%～3%.
7. a kind of method that improves capacitance of lithium secondary battery according to claim 6 is characterized in that: the percentage by weight that described conductive agent consumption accounts for positive active material is 2.1%.
8. a kind of method that improves capacitance of lithium secondary battery according to claim 6, it is characterized in that: described blend step I specifically is meant, in bonding agent, add the solvent that accounts for solvent total amount 50%-70% earlier, stirring makes it dissolving, add the solvent that accounts for solvent total amount 10%-30% again, continue stirring bonding agent is dissolved cmpletely.
9. a kind of method that improves capacitance of lithium secondary battery according to claim 6 is characterized in that: among the described blend step III, fully mixing is that to instigate the viscosity of mixing disposed slurry be 3000～6000mpa.s.
10. a kind of method that improves capacitance of lithium secondary battery according to claim 9, it is characterized in that: described method further comprises after blend step III: the slurry that obtains was vacuumized and stirs 0.2～1 hour, cross 150 mesh sieves then.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100623559A CN101136497B (en) | 2006-08-28 | 2006-08-28 | Method for improving capacitance of lithium secondary battery |
| HK08109775.4A HK1114468A1 (en) | 2006-08-28 | 2008-09-03 | A method for improving the capacity of the lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100623559A CN101136497B (en) | 2006-08-28 | 2006-08-28 | Method for improving capacitance of lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101136497A CN101136497A (en) | 2008-03-05 |
| CN101136497B true CN101136497B (en) | 2011-02-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100623559A Expired - Fee Related CN101136497B (en) | 2006-08-28 | 2006-08-28 | Method for improving capacitance of lithium secondary battery |
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| CN (1) | CN101136497B (en) |
| HK (1) | HK1114468A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752550B (en) * | 2008-12-10 | 2014-01-08 | 深圳市比克电池有限公司 | Method for confecting lithium ion battery anode sizing agent |
| CN102195079B (en) * | 2010-03-12 | 2015-03-04 | 江苏海四达电源股份有限公司 | High-capacity high-power ferrous phosphate lithium power battery and manufacturing method thereof |
| CN102237515B (en) * | 2010-04-20 | 2016-01-06 | 深圳市比克电池有限公司 | Lithium ion battery, positive electrode active materials and preparation method thereof |
| CN102569733B (en) * | 2010-12-21 | 2016-03-09 | 比克国际(天津)有限公司 | The preparation method of pulp of lithium ion battery, cell size and lithium ion battery |
| CN110487665A (en) * | 2019-08-23 | 2019-11-22 | 深圳市比克动力电池有限公司 | A kind of wellability detection method of pole piece |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1532984A (en) * | 2003-03-21 | 2004-09-29 | 比亚迪股份有限公司 | Method for producing lithium ion secondary cell |
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2006
- 2006-08-28 CN CN2006100623559A patent/CN101136497B/en not_active Expired - Fee Related
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- 2008-09-03 HK HK08109775.4A patent/HK1114468A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1532984A (en) * | 2003-03-21 | 2004-09-29 | 比亚迪股份有限公司 | Method for producing lithium ion secondary cell |
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| Publication number | Publication date |
|---|---|
| CN101136497A (en) | 2008-03-05 |
| HK1114468A1 (en) | 2008-10-31 |
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