CN102593413A - Manufacturing method of pole piece for improving current density - Google Patents
Manufacturing method of pole piece for improving current density Download PDFInfo
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- CN102593413A CN102593413A CN2012100124077A CN201210012407A CN102593413A CN 102593413 A CN102593413 A CN 102593413A CN 2012100124077 A CN2012100124077 A CN 2012100124077A CN 201210012407 A CN201210012407 A CN 201210012407A CN 102593413 A CN102593413 A CN 102593413A
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- pole piece
- current density
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- conductive layer
- improves current
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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
Abstract
The invention provides a manufacturing method of a pole piece for improving the current density. The manufacturing method comprises the following steps: step 1, washing a basal body; step 2, preparing conducting layer slurry; step 3, preparing a conducting layer; step 4, preparing active substance slurry; and step 5, coating and making the pole piece. A transitional conducting layer is formed between the basal body and the active substance, so that good rate performance and long cycle life of a lithium iron phosphate battery can be guaranteed after the lithium iron phosphate battery is manufactured by the pole piece manufactured by the manufacturing method.
Description
Technical field
The present invention relates to the lithium ion battery field, be specifically related to a kind of pole piece preparation method who improves current density.
Background technology
The raising that Along with people's requires the energy, lithium ion battery is developed to the maximization direction by miniaturization, and high-energy and high-power lithium ion battery product can emerge successively.Consider the security performance of large-scale lithium ion battery, ferric phosphate lithium cell obtains comprising the approval of user and manufacturing firm, but the high-rate performance of ferric phosphate lithium cell can not satisfy user's needs all the time.In order to solve the high-rate performance of ferric phosphate lithium cell; A lot of scientific research persons start with from the structure and the physical and chemical index that improve LiFePO 4 material; For example through the method for other metal ions that mix, reduce particle grain size etc. through the nanometer metallization processes, these measures have all reached good effect; But the high-rate performance of ferric phosphate lithium cell not only depends on the positive electrode performance, and the manufacturing process of pole piece also has considerable influence to the high-rate performance of ferric phosphate lithium cell.Facts have proved that the good pole piece of high-rate performance requires the content of active material internal sizes less relatively, and that active material and base material two-phase interface require is bonding firm and resistance is little.The preparation method of battery pole piece is through making slurry (containing active material, bonding agent, conductive agent, solvent) in the industry at present; Be coated in matrix surface then, oven dry, compacting; Film-making obtains battery pole piece; This pole piece preparation method does not consider the difference of active material inside and active material and matrix two-phase interface, has the relatively poor LiFePO 4 material of conductivity at two-phase interface, causes poor, the cycle life weak point of ferric phosphate lithium cell high rate performance that utilizes this pole piece to make.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of pole piece preparation method who improves current density; Between matrix and active matter, form the transition conductive layer, the pole piece through this method preparation is used to make the good rate capability that can guarantee this ferric phosphate lithium cell behind the ferric phosphate lithium cell, has extended cycle life.
For solving above-mentioned existing technical problem, the present invention adopts following scheme: a kind of pole piece preparation method who improves current density may further comprise the steps:
Step 1: the cleaning of matrix: the glacial acetic acid solution of employing 30% cleaned 1～10 minute matrix;
Step 2: the preparation of conductive layer slurry: earlier solvent and dispersant are added in the container; Back adding conductive agent stirs; Be stirred to even back and add bonding agent, it is 9 that the back that stirs uses ammoniacal liquor to regulate pH, is stirred to while regulating evenly; Extracting vacuum is removed bubble, and the mass ratio of said conductive agent, solvent, dispersant, bonding agent is 0.1～40: 98～50: 0.5～1.0: 1.4～9.0;
Step 3: the preparation of conductive layer: control silk screen printing thickness is 0.1～10 μ m, the conductive layer slurry that makes in the step 2 is printed on uniformly matrix surface and the drying that makes in the step 1;
Step 4: the preparation of active material slurry: is 35～55: 58～38 with active material, solvent, bonding agent, conductive agent according to mass ratio: 1～6: 6～1 mixed, and the final vacuum that is uniformly dispersed is removed bubble;
Step 5: coating film-making: the active material slurry that makes in the step 4 is coated on the conductive layer surface that makes in the step 3 and oven dry, compacting, film-making uniformly.
As preferably, the matrix in the said step 1 is Copper Foil or aluminium foil.
As preferably, the conductive agent in said step 2 and the step 4 is the one or any several kinds mixture in acetylene black, graphite, Graphene, CNT, the conducting polymer.
As preferably, the solvent in said step 2 and the step 4 is a kind of in N-pyrrolidones, the deionized water or both mixtures.
As preferably, the dispersant in the said step 2 is a tannic acid.
As preferably, the bonding agent in said step 2 and the step 4 is a kind of or any several kinds mixture of inclined to one side polytetrafluoroethylene, polytetrafluoroethylene, polyacrylonitrile, butadiene-styrene rubber, acrylonitrile-butadiene rubber, s-B-S rubber, sodium carboxymethylcellulose, Arabic gum, natural rubber.
Beneficial effect:
The present invention adopts technique scheme that a kind of pole piece preparation method who improves current density is provided; Between matrix and active matter, form the transition conductive layer, the pole piece through this method preparation is used to make the good rate capability that guaranteed this ferric phosphate lithium cell behind the ferric phosphate lithium cell, has extended cycle life.
Description of drawings
Fig. 1 is the structural representation of the matrix behind the silk screen printing conductive layer among the present invention;
Fig. 2 is the surface picture of the matrix behind the silk screen printing conductive layer among the present invention;
Fig. 3 is for after the pole piece of the pole piece that adopts the present invention's preparation and common process preparation is respectively applied for the manufacturing battery, the AC impedance comparison diagram of battery;
Fig. 4 is for after the pole piece of the pole piece that adopts the present invention's preparation and common process preparation is respectively applied for the manufacturing battery, the correlation curve figure of battery battery capacity conservation rate under the discharge of different multiplying;
After the pole piece that Fig. 5 prepares for employing the present invention is used to make battery, the curve chart of battery battery capacity conservation rate under different cycle-indexes.
Embodiment
Embodiment one:
A kind of pole piece preparation method who improves current density may further comprise the steps: the aluminium foil of 20 μ m was immersed in the glacial acetic acid after 2 minutes, and subsequent use through oven drying, the purpose of cleaning is for the greasy dirt of removing matrix surface, increases the specific area of matrix; After taking by weighing 7.00kg deionized water, 1.00kgN-pyrrolidones and 0.06kg tannic acid mixing and stirring, add 0.84kg flake graphite and 0.30kg electrically conductive graphite, stir, add 0.80kg polytetrafluoroethylene powder, vacuumize after being uniformly dispersed; Regulate the print thickness of screen process press, and after examination prints successfully, with the uniform silk-screen of conductive layer slurry on aluminium foil; Keeping print thickness is 0.5 μ m; And dry (structure of the matrix behind the silk screen printing conductive layer is as shown in Figure 1, and wherein 1 is aluminium foil, and 2 is conductive layer; Matrix surperficial as shown in Figure 2); The configuration of active matter slurry vacuumizes after evenly according to 22.00kg LiFePO4,24.00kg deionized water, 1.00kgN-pyrrolidones, 1.50kg polytetrafluoroethylene, 1.10kg graphite, 0.40kg acetylene black mixed and dispersed; The active matter slurry is coated on above the conductive layer, and oven dry, compacting, film-making.
Producing electric energy, the time revert to the pole plate material of stock blend again in charging through chemical reaction when active material is meant battery discharging, is exactly the active material of negative material such as lithium metal in lithium battery.
The contrast of the pliability of the pole piece of the pole piece of the present invention's preparation and common process preparation is as shown in table 1:
Table 1
Pole piece is more soft, and the internal stress of pole piece is more little, helps pole piece and in assembling process, maintains the original state and be assembled into flawless battery.In the contrast of pliability (number of times that occurs slight crack even destruction until pole piece), the doubling number of times is many more, and the pole piece flexibility is good more.
As shown in Figure 3, for after the pole piece of the pole piece that adopts the present invention's preparation and common process preparation is respectively applied for the manufacturing battery, the AC impedance comparison diagram of battery.The internal resistance of measuring battery through balancing circuitry can not reflect the situation of anode pole piece internal resistance, is to have adopted AC impedance to simulate the numerical value of anode pole piece internal driving among Fig. 3.Among Fig. 3, what the semicircle of high frequency region reflected is the caused impedance of charge transfer at electrolyte/oxide electrode interface, obtains this resistance value through simulation and is respectively 2.8m Ω and 4.2m Ω, and obviously the pole piece interface impedance through patent preparation of the present invention obviously reduces.
Fig. 4 is for after the pole piece of the pole piece that adopts the present invention's preparation and common process preparation is respectively applied for the manufacturing battery, the correlation curve figure of battery battery capacity conservation rate under the discharge of different multiplying.After can finding out that by Fig. 4 the pole piece that adopts the present invention's preparation is used to make battery, battery battery capacity conservation rate under the discharge of different multiplying is high.After the pole piece that Fig. 5 prepares for employing the present invention is used to make battery, the curve chart of battery battery capacity conservation rate under different cycle-indexes.
Embodiment two:
A kind of pole piece preparation method who improves current density may further comprise the steps: the aluminium foil of 20 μ m was immersed in the glacial acetic acid after 2 minutes, and subsequent use through oven drying; After taking by weighing 7.40kg deionized water, 0.80kgN-pyrrolidones and 0.06kg tannic acid mixing and stirring, add 0.64kg flake graphite and 0.60kg electrically conductive graphite, stir, add the inclined to one side polytetrafluoroethylene of 0.80kg, vacuumize after being uniformly dispersed; Regulate the print thickness of screen process press, after examination was printed successfully, on aluminium foil, keeping print thickness was 1.0 μ m with the uniform silk-screen of conductive layer slurry, and dry; The active matter slurry is coated on above the conductive layer, and oven dry, compacting, film-making.
Embodiment three:
A kind of pole piece preparation method who improves current density may further comprise the steps: the aluminium foil of 20 μ m was immersed in the glacial acetic acid after 2 minutes, and subsequent use through oven drying; After taking by weighing 7.40kg deionized water, 0.80kgN-pyrrolidones and 0.06kg tannic acid mixing and stirring; Add 0.64kg flake graphite and 0.60kg electrically conductive graphite; Stir; Add 0.90kg L133 (acrylonitrile-butadiene rubber of Chengdu Yindile Power Source Science and Technology Co., Ltd's manufacturing and the mixture of butadiene-styrene rubber), vacuumize after being uniformly dispersed; Regulate the print thickness of screen process press, and after trying to print successfully, on aluminium foil, keeping print thickness is 1.5 μ m with the uniform silk-screen of conductive layer slurry, and dry; The active matter slurry is coated on above the conductive layer, and oven dry, compacting, film-making.
Have following advantage after pole piece through the present invention preparation is used to make battery: 1, because graphite is layer structure, in bedding angle slippage can take place, the pliability of pole piece is effectively improved; 2, through interfacial conductive layer and active material internal diversityization, the internal resistance of cell diminishes; 3, because the reducing of internal resistance, the polarization of battery rate charge-discharge reduces, and the battery high rate performance improves; 4, the stress that produces in the pucker & bloat process of pole piece in the battery charge and discharge process can cause peeling off of two-phase interface.The existence of conductive layer has formed a kind of transition zone between matrix and active material layer, effectively prevent the damage of two-phase interface, and cycle performance of battery improves.
Claims (6)
1. pole piece preparation method who improves current density is characterized in that: may further comprise the steps:
Step 1: the cleaning of matrix: the glacial acetic acid solution of employing 30% cleaned 1～10 minute matrix;
Step 2: the preparation of conductive layer slurry: earlier solvent and dispersant are added in the container; Back adding conductive agent stirs; Be stirred to even back and add bonding agent, it is 9 that the back that stirs uses ammoniacal liquor to regulate pH, is stirred to while regulating evenly; Extracting vacuum is removed bubble, and the mass ratio of said conductive agent, solvent, dispersant, bonding agent is 0.1～40: 98～50: 0.5～1.0: 1.4～9.0;
Step 3: the preparation of conductive layer: control silk screen printing thickness is 0.1～10 μ m, the conductive layer slurry that makes in the step 2 is printed on uniformly matrix surface and the drying that makes in the step 1;
Step 4: the preparation of active material slurry: is 35～55: 58～38 with active material, solvent, bonding agent, conductive agent according to mass ratio: 1～6: 6～1 mixed, and the final vacuum that is uniformly dispersed is removed bubble;
Step 5: coating film-making: the active material slurry that makes in the step 4 is coated on the conductive layer surface that makes in the step 3 and oven dry, compacting, film-making uniformly.
2. a kind of pole piece preparation method who improves current density according to claim 1, it is characterized in that: the matrix in the said step 1 is Copper Foil or aluminium foil.
3. a kind of pole piece preparation method who improves current density according to claim 1 is characterized in that: the conductive agent in said step 2 and the step 4 is the one or any several kinds mixture in acetylene black, graphite, Graphene, CNT, the conducting polymer.
4. a kind of pole piece preparation method who improves current density according to claim 1 is characterized in that: the solvent in said step 2 and the step 4 is a kind of in N-pyrrolidones, the deionized water or both mixtures.
5. a kind of pole piece preparation method who improves current density according to claim 1, it is characterized in that: the dispersant in the said step 2 is a tannic acid.
6. a kind of pole piece preparation method who improves current density according to claim 1 is characterized in that: the bonding agent in said step 2 and the step 4 is a kind of or any several kinds mixture of inclined to one side polytetrafluoroethylene, polytetrafluoroethylene, polyacrylonitrile, butadiene-styrene rubber, acrylonitrile-butadiene rubber, s-B-S rubber, sodium carboxymethylcellulose, Arabic gum, natural rubber.
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| CN2012100124077A CN102593413A (en) | 2012-01-16 | 2012-01-16 | Manufacturing method of pole piece for improving current density |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903892A (en) * | 2012-10-18 | 2013-01-30 | 江苏富朗特新能源有限公司 | Method for manufacturing industrial energy storage type lithium battery pole piece |
| CN103165899A (en) * | 2012-12-07 | 2013-06-19 | 深圳市海太阳实业有限公司 | Positive pole piece and preparation method thereof and battery |
| CN103413693A (en) * | 2013-05-24 | 2013-11-27 | 宁波南车新能源科技有限公司 | Method of manufacturing a supercapacitor |
| CN103956460A (en) * | 2014-04-15 | 2014-07-30 | 洛阳月星新能源科技有限公司 | Method for prolonging cyclic service life of lithium iron phosphate battery |
| CN103972471A (en) * | 2014-04-19 | 2014-08-06 | 东风商用车有限公司 | Positive pole piece of large multiplying power lithium iron phosphate battery and preparation method thereof |
| CN104388996A (en) * | 2014-10-30 | 2015-03-04 | 苏州禾川化学技术服务有限公司 | Black hole liquid and preparation method thereof |
| CN105406077A (en) * | 2015-11-24 | 2016-03-16 | 青岛能迅新能源科技有限公司 | Nanoscale conductive coating material of lithium ion battery positive electrode and preparation method therefor |
| CN114388725A (en) * | 2020-10-21 | 2022-04-22 | 深圳格林德能源集团有限公司 | Lithium ion battery positive pole piece and preparation method thereof |
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| CN102034981A (en) * | 2010-10-26 | 2011-04-27 | 东莞新能源科技有限公司 | Collector used for negative pole of lithium ion battery |
| US20110159376A1 (en) * | 1999-11-23 | 2011-06-30 | Sion Power Corporation | Protection of anodes for electrochemical cells |
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| CN101174685A (en) * | 2007-10-26 | 2008-05-07 | 中南大学 | Anode or cathode pole piece of lithium ion battery and coating method thereof |
| CN101262054A (en) * | 2008-03-24 | 2008-09-10 | 万向集团公司 | Production technology for polymer lithium battery anode and cathode slice |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903892A (en) * | 2012-10-18 | 2013-01-30 | 江苏富朗特新能源有限公司 | Method for manufacturing industrial energy storage type lithium battery pole piece |
| CN103165899A (en) * | 2012-12-07 | 2013-06-19 | 深圳市海太阳实业有限公司 | Positive pole piece and preparation method thereof and battery |
| CN103413693A (en) * | 2013-05-24 | 2013-11-27 | 宁波南车新能源科技有限公司 | Method of manufacturing a supercapacitor |
| CN103413693B (en) * | 2013-05-24 | 2016-01-13 | 宁波南车新能源科技有限公司 | A kind of manufacture method of ultracapacitor |
| CN103956460A (en) * | 2014-04-15 | 2014-07-30 | 洛阳月星新能源科技有限公司 | Method for prolonging cyclic service life of lithium iron phosphate battery |
| CN103956460B (en) * | 2014-04-15 | 2016-03-16 | 洛阳月星新能源科技有限公司 | A kind of method for improving ferric phosphate lithium cell service life cycle |
| CN103972471A (en) * | 2014-04-19 | 2014-08-06 | 东风商用车有限公司 | Positive pole piece of large multiplying power lithium iron phosphate battery and preparation method thereof |
| CN104388996A (en) * | 2014-10-30 | 2015-03-04 | 苏州禾川化学技术服务有限公司 | Black hole liquid and preparation method thereof |
| CN105406077A (en) * | 2015-11-24 | 2016-03-16 | 青岛能迅新能源科技有限公司 | Nanoscale conductive coating material of lithium ion battery positive electrode and preparation method therefor |
| CN114388725A (en) * | 2020-10-21 | 2022-04-22 | 深圳格林德能源集团有限公司 | Lithium ion battery positive pole piece and preparation method thereof |
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Application publication date: 20120718 |