CN101894944B - Method for preparing lithium ion battery pole pieces - Google Patents
Method for preparing lithium ion battery pole pieces Download PDFInfo
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- CN101894944B CN101894944B CN2010102364470A CN201010236447A CN101894944B CN 101894944 B CN101894944 B CN 101894944B CN 2010102364470 A CN2010102364470 A CN 2010102364470A CN 201010236447 A CN201010236447 A CN 201010236447A CN 101894944 B CN101894944 B CN 101894944B
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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 novel method for preparing lithium ion battery pole pieces. The method mainly comprises the following operational steps of: preparing a feeding material by mixing; precisely measuring the feeding material and performing injection molding on the feeding material onto a current collector with an injection molding machine; and compacting the feeding material with a compactor. The raw materials consist of powder and glue, wherein the powder consists of an anode active material or a cathode active material, and a conductive agent; the glue consists of an adhesive and an addition agent; and the ratio of the powder to the glue is 4 to 32:1. The lithium ion battery pole pieces prepared by the method and lithium ion batteries have the advantages of low manufacturing cost, high uniformity and repeatability of the pole pieces, high compaction density of the pole pieces, high volumetric capacity of the batteries and the like.
Description
Technical field
The invention belongs to the lithium ion battery field, relate to a kind of preparation method of electrodes of lithium-ion batteries and with the electrodes of lithium-ion batteries of the method preparation and the lithium ion battery for preparing with this pole piece.
Background technology
Lithium ion battery has occupied the leading role status as high power capacity, high-output power, light secondary cell in the markets such as mobile phone, notebook computer, video camera, become the main power source of small-sized electronic product.Along with minimizing even the exhaustion of petroleum-based energy, lithium ion battery will be played the part of important role in power source.
At present lithium ion battery all is to prepare pole piece by techniques such as homogenate, coatings, has used a large amount of organic solvents in the slurry process, and these organic solvents vapor away in the pole piece dry run, has not only polluted environment but also has increased the cost of battery.The factors such as vibration of the character of slurry, the parameter of coating, coating machine make the pole piece became uneven that obtains even, and this inhomogeneous the inhomogeneous of battery performance of causing of pole piece has influence on life-span of rate of finished products and the battery pack of battery pack combo.
Summary of the invention
The invention provides a kind of preparation method of brand-new electrodes of lithium-ion batteries, its main operational steps is: by mixing preparation feeding, with injection moulding machine feeding is carried out delicate metering and be injected on the collector, by the spreader bar compacting.
One aspect of the present invention provides a kind of preparation method of electrodes of lithium-ion batteries, the method to comprise successively to get the raw materials ready, the technical process by mixing preparation feeding, injection moulding, drying, compressing tablet.
According to a concrete but nonrestrictive embodiment of the present invention, in material preparation step, the used raw material of preparation pole piece is comprised of powder and glue, and wherein powder is comprised of negative or positive electrode active material and conductive agent, glue is comprised of bonding agent and additive, and the ratio of powder and glue is 4～32: 1.A preferred embodiment is the shared mass percent of each component in the powder:
The negative or positive electrode active material: 85～98%, conductive agent: 2～15%; The shared mass percent of each component in the glue: bonding agent: 80～96%, additive: 4～20%.
According to a concrete but nonrestrictive embodiment of the present invention, positive active material is lamellar compound, and its chemical formula is LiMO
2, wherein M is Ni, Mn, one or more among the Co; Spinel compound, its chemical formula are LiMn
2O
4Olivine structural material, its chemical formula are LiFePO
4Or the modified material of above-mentioned substance or one or more combinations in the above-mentioned substance;
Negative electrode active material is Carbon Materials or transition metal oxide or their combination;
Conductive agent is one or more the combination in electrically conductive graphite, acetylene black and the conducting polymer substance;
Bonding agent is one or more thermoplastic resins;
Additive is one or more the combination in glycerol, castor oil, oleic acid, the nonionic soil temperature.
According to a concrete but nonrestrictive embodiment of the present invention, mixing is to carry out in mixing roll, and mixing temperature is 80～350 ℃, and the mixing time is 7～24 hours.
According to a concrete but nonrestrictive embodiment of the present invention, injection moulding is to finish with injection molding machine, and the temperature of injection moulding is 80～350 ℃, and the pressure of injection moulding is 20～140Mpa.
According to a concrete but nonrestrictive embodiment of the present invention, the drying of pole piece is 100～200 ℃ of vacuumizes, and the time is 10～20 hours.
According to a concrete but nonrestrictive embodiment of the present invention, the used equipment of compressing tablet is spreader bar, and pressure is 20～200MPa.
Another aspect of the present invention provides a kind of electrodes of lithium-ion batteries, and described pole piece is to be prepared by above-mentioned method.
Another aspect of the present invention provides a kind of lithium ion battery, and described lithium ion battery comprises the positive and negative electrode battery pole piece, barrier film and electrolyte, and wherein said positive and negative electrode battery pole piece is the electrodes of lithium-ion batteries that is prepared by said method.
The preparation method of electrodes of lithium-ion batteries provided by the invention and according to the electrodes of lithium-ion batteries of the method preparation and and then the lithium ion battery made have following advantage: during the preparation feeding because there not being with an organic solvent to greatly reduce the cost of making battery, adopt precise injection machine thereby the precision control of shot to be improved homogeneity and the repeatability of pole piece, adopt the spreader bar compacting, greatly improve the compacted density of pole piece, improved the volume capacity of battery.
Description of drawings
Fig. 1 carries out the monocell cyclic curve that charge and discharge cycles obtains after making battery with electrodes of lithium-ion batteries of the present invention among the embodiment 2.
Embodiment
Hereinafter provide concrete execution mode to further specify the present invention, but the present invention is not limited only to following execution mode.
Unless additionally point out, the proportionate relationship between the component that the context of the invention is mentioned is all in unit of weight.
Of the present invention one concrete but the execution mode of indefiniteness has provided a kind of method for preparing electrodes of lithium-ion batteries, the method may further comprise the steps:
1. get the raw materials ready
The required raw material of preparation pole piece is comprised of powder and two parts of glue, and wherein powder is comprised of active material and conductive agent, and glue is comprised of bonding agent and additive.The ratio of powder and glue is 4～32: 1.
More particularly, the shared mass percent of each component is as follows in the powder:
Active material: 85～98%, conductive agent: 2～15%;
The shared quality percentage of each component is as follows in the glue:
Bonding agent: 80～96%, additive: 4～20%.
Wherein, active material comprises positive active material and negative electrode active material.Positive active material as: lamellar compound, its chemical formula are LiMO
2, wherein M is Ni, Mn, one or more among the Co; Spinel compound, its chemical formula are LiMn
2O
4Olivine structural material, its chemical formula are LiFePO
4The perhaps modified material of above-mentioned substance or one or more combinations in the above-mentioned substance.Negative electrode active material comprises Carbon Materials or transition metal oxide, and Carbon Materials can be such as native graphite, electrographite, charcoal fiber, amorphous carbon; Transition metal oxide is LiTiO
4Perhaps Li
4Ti
5O
12
Conductive agent can be one or more the combination in electrically conductive graphite, acetylene black and the conducting polymer substance.
Bonding agent can be thermoplastic resin, such as one or more the combination in polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), the butadiene-styrene latex (SBR).
Additive can be glycerol, castor oil, oleic acid, nonionic soil temperature etc.The adding of additive can effectively improve the flowability of feeding, is easy to make the feeding of uniformity.
2. by mixing preparation feeding
Above-mentioned raw materials can carry out mixing, mixing temperature in mixing roll be 80～350 ℃, and the mixing time is 7～24 hours.
The technical scheme of comparative optimization is, in the hopper of mixing roll, add bonding agent, under 100～350 ℃ of temperature mixing 1～4 hour, add additive, mixing 1～4 hour, add active material, continued mixing 1～4 hour, added conductive agent mixing 4～12 hours, mixing end, after cooling, it is broken to put into disintegrating machine, makes feeding.
In order to simplify processing step, a kind of substituting technical scheme is that bonding agent and additive can be synchronously mixing 1～4 hour, needn't be mixing step by step; Active material and conductive agent also can be synchronously mixing 4～12 hours, needn't be mixing step by step.
3. injection moulding, drying, compressing tablet
Feeding is injected into contains in the collector die cavity, controlling the active material bed thickness by the size of die cavity is 60～300 microns, accurately control shot with the precision injection molding machine, the temperature of injection moulding is controlled at 80～350 ℃, and the pressure of injection moulding is controlled at 20～140Mpa.Pole piece in 100～200 ℃ of vacuum drying chambers after dry 10～20 hours, is pressed into 60～150 microns pole piece at spreader bar.Can control by regulating pressure the thickness of pole piece, pressure is generally 20～200MPa.Also can control pole piece thickness with industrial other conventional meanses, as regulating pole piece thickness by stroke and distance.
The electrodes of lithium-ion batteries that above-mentioned technique makes, by adding barrier film, the coiling fluid injection is made lithium ion battery according to conventional method.
The electrodes of lithium-ion batteries that utilizes above-mentioned technique to make mainly contains following effect:
1. pole piece smooth surface and softness, the pole piece thickness is even.
2. do not use a large amount of organic solvents when preparing feeding, reduced cost.
3. improved the rate of finished products of battery, and technique is simple, easy to operate, be convenient to suitability for industrialized production.
The present invention will be further elaborated below in conjunction with concrete example, but can not be interpreted as limitation of the present invention.
Embodiment 1
Accurately taking by weighing 5.00 kilograms of polytetrafluoroethylene joins in the mixing roll mixing 4 hours at 300 ℃, taking by weighing 0.25 kilogram of glycerol and 0.25 kilogram of POLYSORBATE 80 joins and continues after mixing 4 hours in the mixing roll, in mixing roll, added 56.00 kilograms of LiFePO4s mixing 4 hours, add 2.00 kilograms of crystalline flake graphites and 1.00 kilograms of acetylene blacks, continue cooling after mixing 6 hours, pulverize and make anodal feeding.Accurately take by weighing 2.00 kilograms of polytetrafluoroethylene and join in the mixing roll at 300 ℃ after mixing 4 hours, added 0.10 kilogram of glycerol and 0.10 kilogram of POLYSORBATE 80 mixing 2 hours.Added 36.00 kilograms in negative pole graphite in the mixing roll mixing 4 hours, and added 0.80 kilogram of 1.50 kilograms of acetylene blacks and electrically conductive graphite and continue cooling after mixing 6 hours, pulverize and obtain the negative pole feeding.The iron phosphate lithium positive pole feeding is injected in the die cavity that contains aluminum foil current collector with precise injection machine, injection temperature is 300 ℃, and pressure is 60MPa, and thickness is 250 microns; The negative pole feeding is injected into and contains in the Copper Foil collector die cavity, and injection temperature is 300 ℃, and pressure is 60MPa, and thickness is 160 microns.Pole piece after 10 hours, is used spreader bar compacting pole piece 120 ℃ of vacuumizes, and the thickness that makes anode pole piece is 140 microns, and the thickness of cathode pole piece is 110 microns.
In order to contrast the pliability of pole piece, the pole piece of the pole piece that adopts the present invention's preparation and the preparation of common coating processes has been carried out the bending contrast test, be bent to number of times that fracture appears in pole piece and weigh the pliability of pole piece, it is better that the more and pole piece of bending number of times is not lost explanation pole piece pliability.The result is as showing:
Find out that from upper table the pliability of the pole piece of the present invention's preparation obviously is better than the pole piece of common coating processes preparation.
Embodiment 2
Accurately taking by weighing 5.00 kilograms of polytetrafluoroethylene joins in the mixing roll mixing 4 hours at 300 ℃, taking by weighing 0.25 kilogram of glycerol and 0.25 kilogram of POLYSORBATE 80 joins and continues after mixing 4 hours in the mixing roll, in mixing roll, added 56.00 kilograms of LiFePO4s mixing 4 hours, add 2.00 kilograms of crystalline flake graphites and 1.00 kilograms of acetylene blacks, continue cooling after mixing 6 hours, pulverize and make anodal feeding.Accurately take by weighing 2.00 kilograms of polytetrafluoroethylene and join in the mixing roll at 300 ℃ after mixing 4 hours, added 0.10 kilogram of glycerol and 0.10 kilogram of POLYSORBATE 80 mixing 2 hours.Added 36.00 kilograms in negative pole graphite in the mixing roll mixing 4 hours, and added 0.80 kilogram of 1.50 kilograms of acetylene blacks and electrically conductive graphite and continue cooling after mixing 6 hours, pulverize and obtain the negative pole feeding.Anodal feeding is injected in the die cavity that contains aluminum foil current collector with precise injection machine, injection temperature is 300 ℃, and pressure is 60MPa, and thickness is 250 microns, and coating content is 31.00g; The negative pole feeding is injected in the die cavity that contains the Copper Foil collector, and injection temperature is 300 ℃, and pressure is 60MPa, and thickness is 160 microns, and coating content is 16.00g.Pole piece after 10 hours, is used spreader bar compacting pole piece 120 ℃ of vacuumizes, and the thickness that makes anode pole piece is 140 microns, and the thickness of cathode pole piece is 110 microns.Then add barrier film, battery is made in the coiling fluid injection, does charge and discharge cycles in room temperature with 1C.Fig. 1 carries out the monocell cyclic curve that charge and discharge cycles obtains.As can be seen from the figure, the good cycle of battery, efficiency for charge-discharge is high.Comparative experimental example:
Accurately take by weighing 85.00 kilograms of 56.00 kilograms of LiFePO4s, 1.00 kilograms, 2.00 kilograms crystalline flake graphites of acetylene black, PVDF5.00 kilogram, 1-METHYLPYRROLIDONE (NMP), be mixed with anode sizing agent by vacuum stirring, make anode pole piece with coating process, coating content is 31.00 ± 2.00g; Accurately take by weighing 50.00 kilograms of 36.00 kilograms of negative pole graphite, 2.50 kilograms of acetylene blacks, CMC0.50 kilogram, 1.10 kilograms of SBR, deionized waters, be mixed with cathode size by vacuum stirring, make cathode pole piece with coating process, coating content is 18.00 ± 1.00g.Then add barrier film, battery is made in the coiling fluid injection, does charge and discharge cycles in room temperature with 1C.Comparing result is as follows:
Maximum characteristics of the present invention are exactly that deviation between the pole piece is very little, are particularly suitable for being applied to the string of the battery pack in the electrokinetic cell also, and the combo rate improves greatly.
Below only be concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
Claims (6)
1. the preparation method of an electrodes of lithium-ion batteries is characterized in that, the used raw material of the method is comprised of powder and glue, and the mass ratio of powder and glue is 4～32: 1; Wherein powder is comprised of negative or positive electrode active material and conductive agent, the shared mass percent of each component in the powder: negative or positive electrode active material: 85～98%, and conductive agent: 2～15%; Glue is comprised of bonding agent and additive, the shared mass percent of each component in the glue: bonding agent: 80～96%, and additive: 4～20%, wherein, described additive is one or more the combination in glycerol, castor oil, oleic acid, the nonionic soil temperature; Described method comprises following processing step:
By mixing preparation feeding, with raw material in mixing roll mixing 7～24 hours, mixing temperature was 80～350 ℃, after the cooling, makes feeding through fragmentation;
Injection moulding is accurately controlled shot with the precision injection molding machine, feeding is injected into contains in the collector die cavity, and the temperature of injection moulding is 80～350 ℃, and the pressure of injection moulding is 20～140Mpa;
Drying, with the pole piece after the injection moulding 100～200 ℃ of vacuumizes 10～20 hours;
Compressing tablet, compressing under the pressure of 20～200MPa with spreader bar.
2. according to claim 1 described method, wherein, positive active material is lamellar compound, its chemical formula is LiMO
2, wherein M is Ni, Mn, one or more among the Co; Spinel compound, its chemical formula are LiMn
2O
4Olivine structural material, its chemical formula are LiFePO
4Or the modified material of above-mentioned substance or one or more combinations in the above-mentioned substance;
Negative electrode active material is Carbon Materials or transition metal oxide or their combination;
Conductive agent is one or more the combination in electrically conductive graphite, acetylene black and the conducting polymer substance;
Bonding agent is one or more thermoplastic resins.
3. according to claim 1 and 2 method wherein, in the preparation feeding procedure, adds first bonding agent, under 100～350 ℃ of temperature mixing 1～4 hour, add again additive, mixing 1～4 hour, add again active material, mixing 1～4 hour, added at last conductive agent mixing 4～12 hours.
4. according to claim 1 and 2 method, wherein, in the preparation feeding procedure, bonding agent and additive mixing 1～4 hour synchronously add active material and conductive agent, synchronous mixing 4～12 hours afterwards.
5. an electrodes of lithium-ion batteries is characterized in that, described pole piece is by preparing such as arbitrary described method among the claim 1-4.
6. a lithium ion battery comprises the positive and negative electrode battery pole piece, and barrier film and electrolyte is characterized in that, described positive and negative electrode battery pole piece is electrodes of lithium-ion batteries claimed in claim 5.
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| CN2010102364470A CN101894944B (en) | 2010-07-26 | 2010-07-26 | Method for preparing lithium ion battery pole pieces |
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| CN2010102364470A CN101894944B (en) | 2010-07-26 | 2010-07-26 | Method for preparing lithium ion battery pole pieces |
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| CN103551571B (en) * | 2013-11-08 | 2016-10-05 | 侯春平 | A kind of lithium ion battery negative material sinter burden equipment |
| CN115064699B (en) * | 2022-07-29 | 2023-08-11 | 苏州清陶新能源科技有限公司 | Negative electrode plate, lithium ion battery and preparation method of lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4320185A (en) * | 1981-01-19 | 1982-03-16 | Mpd Technology Corporation | Production of a cell electrode system |
| CN1819321A (en) * | 2006-03-06 | 2006-08-16 | 深圳市力多威电池有限公司 | Lithium ion battery with high multiplying factor |
| CN1838999A (en) * | 2003-07-09 | 2006-09-27 | 麦斯韦尔技术股份有限公司 | Dry particle based electrochemical apparatus and methods of making same |
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| US6589299B2 (en) * | 2001-02-13 | 2003-07-08 | 3M Innovative Properties Company | Method for making electrode |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4320185A (en) * | 1981-01-19 | 1982-03-16 | Mpd Technology Corporation | Production of a cell electrode system |
| CN1838999A (en) * | 2003-07-09 | 2006-09-27 | 麦斯韦尔技术股份有限公司 | Dry particle based electrochemical apparatus and methods of making same |
| CN1819321A (en) * | 2006-03-06 | 2006-08-16 | 深圳市力多威电池有限公司 | Lithium ion battery with high multiplying factor |
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