CN1728427A - Adhesion agent of anode, pulp for anode obtained, lithium battery ,and preparation method - Google Patents
Adhesion agent of anode, pulp for anode obtained, lithium battery ,and preparation method Download PDFInfo
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- CN1728427A CN1728427A CNA200410050866XA CN200410050866A CN1728427A CN 1728427 A CN1728427 A CN 1728427A CN A200410050866X A CNA200410050866X A CN A200410050866XA CN 200410050866 A CN200410050866 A CN 200410050866A CN 1728427 A CN1728427 A CN 1728427A
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- adhesive
- anode
- sizing agent
- lithium battery
- anode sizing
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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 disclosed adhesion agent contains Teflon, water as well as one or more materials in cellulose ethers with viscosity in 1500-10000 centipoises. The adhesion agent does not contain organic solvent, which is utilized in traditional adhesion agent necessarily, and raises performances of positive pole piece in lithium battery. The invention also discloses pulp for anode. The pulp includes active material, current conducting agent and the said adhesion agent. Moreover, the invention discloses lithium battery of using the pulp for anode, and preparation method. Comparing with existed lithium batteries, the disclosed lithium battery possesses better parameter of specific capacity of anode mass and parameter of battery capacity.
Description
Technical field
The present invention relates to a kind of lithium battery with adhesive, adopt this adhesive slurry, adopt lithium battery of this slurry and preparation method thereof, more particularly, the present invention relates to a kind of method for preparing the adhesive that lithium battery anode uses, the anode sizing agent that adopts this adhesive, adopts the lithium battery of this anode sizing agent and prepare this lithium battery.
Background technology
At present, the anode sizing agent of lithium ion battery contains active material, conductive agent, adhesive usually, can also contain some conductive additive.Because lithium ion battery is not soluble in water usually with the main component of anodal adhesive, therefore need to adopt organic solvent usually, for example, NMP (N-methyl pyrrolidone), dimethylacetylamide etc.Match the high molecular bonding that uses with these organic solvents with material PVDF (Kynoar) normally.Adopt organic solvent that many shortcomings are arranged: (1) because the organic solvent that is adopted has certain toxicity, thereby, must be in apparatus for coating with solvent recovering system, could guarantee the gas compliance with environmental protection requirements after the process recovery.(2) because organic solvent is inflammable, explosive, apparatus for coating not only will be provided with solvent recovering system, also must on its heating system explosion-protection equipment be set.And this heating system generally adopts the deep fat mode to heat.Because this heating system need be added boiler plant deep fat is provided, make power cost strengthen, the complicated and control difficulty of equipment.(3) organic solvent very easily absorbs air moisture, and pole piece caking property descends after absorbing water, and has a strong impact on cycle performance of battery, thereby must the strict humidity of controlling environment when preparing slurry.(4) cost of organic solvent is higher, causes battery cost to rise.China patent application CN00117141.0 discloses a kind of lithium ion battery and has sticked with glue agent, and this adhesive has adopted coupling agent modified Kynoar, has used organic solvent in the slurry.The technical scheme of this patent application just has these above-mentioned defectives.
In the prior art, the someone has adopted polytetrafluoroethylene as the bonding material of using.For example, China's patent application CN96114275.8 discloses a kind of with the manufacture method of PTFE (polytetrafluoroethylene) for the lithium ion battery of bonding usefulness material.Though polytetrafluoroethylene is more much better than other bonding character with material, the simple obtained anode sizing agent coating performance of the adhesive instability that adopts polytetrafluoroethylene makes the anode pole piece that makes that the shortcoming that is difficult to control of quality be arranged.
Therefore, be necessary to develop a kind of toxicity and inflammable and explosive problem that can solve organic solvent, have the anode sizing agent of good coating performance again, thereby further improve the performance of lithium battery.
Summary of the invention
One of purpose of the present invention provides a kind of adhesive that lithium battery anode is used for preparing, and does not contain organic solvent in this adhesive, can there be inflammable and explosive problem in people's toxigenicity, and this adhesive can improve the coating performance of anode sizing agent.
Adhesive of the present invention also contains one or more cellulose ethers materials except containing polytetrafluoroethylene and water, the viscosity of adhesive is between the 1500-10000 centipoise.
Polytetrafluoroethylene mainly plays cementation.The cellulose ethers material has good water-solubility, and is soluble in water, has antisolvent precipitation, emulsifying dispersivity and is difficult for character such as corrupt, harmless, can be used as thickener, adhesive, suspending agent, solid dispersion etc.Cellulose ethers material of the present invention can be selected from one or more in hydroxyethylcellulose (HEC), methylcellulose (MC), hydroxypropyl cellulose (HPC), hydroxypropyl methylcellulose (HPMC), the sodium carboxymethylcellulose (CMCNa), but more above-mentioned these materials of performance are superior in every respect owing to sodium carboxymethylcellulose, therefore, preferably adopt sodium carboxymethylcellulose.The weight ratio of polytetrafluoroethylene in this adhesive and cellulose ethers material is preferably 1-6: 1.
Used water preferably adopts the deionized water of conductivity below 3 μ S/cm in the adhesive of the present invention.Though the solvent that common water can be used as in the adhesive uses, its effect can not show a candle to deionized water.Reason is: contain various inorganic salts in the light water, the metal ion of these inorganic salts can produce bigger influence to the voltage of battery, thereby has influence on the performance of battery, and the metal ion that contains in the water is many more, and the conductance of water is just big more.Therefore, be necessary the conductance to control water, we find that the solvent that the following deionized water of 3 μ S/cm is suitable as in the adhesive uses.
The adhesive that preparation lithium battery anode of the present invention is used has not only remedied the deficiency that the adhesive of traditional positive pole usefulness must be with an organic solvent, has adopted environmental protection formulae, and has made the performance of lithium battery anode pole piece obtain improving further.
Two of purpose of the present invention provides a kind of anode sizing agent that lithium battery anode is used for preparing, and this slurry does not contain the machine solvent and has good coating performance.
Anode sizing agent of the present invention not only comprises active material, conductive agent and adhesive, also comprises above-mentioned adhesive; Wherein, active material can be to be selected from a kind of material in lithium and the formed composite oxides of transition metal or the mixture of several materials, and conductive agent can be to be selected from a kind of material in acetylene black, crystalline flake graphite, carbon black, the carbon fiber or the mixture of several materials.
Preferably, the percentage composition of each component is calculated by weight percentage in the anode sizing agent of the present invention, conductive agent accounts for 3%～10% of anode sizing agent total amount, active material accounts for anode sizing agent total amount 85%～93%, polytetrafluoroethylene accounts for anode sizing agent total amount 3%～7%, the cellulose ethers material accounts for anode sizing agent total amount 1%～3%, and surplus is a water.
For the coating performance that guarantees that anode sizing agent is good, the viscosity of slurry should be moderate, and preferably, its viscosity is controlled at about 2500～15000 centipoises, more preferably, is controlled at about 3000～12000 centipoises.
The conductive agent of anode sizing agent of the present invention can be a kind of material in acetylene black, crystalline flake graphite, carbon black, the carbon fiber or the mixture of several materials, can also be other electric conducting materials in being used as lithium battery anode slurry.The present invention preferably adopts acetylene black and/or crystalline flake graphite, more preferably, adopts acetylene black.The conductive agent ratio is generally 3%～10% in the anode sizing agent.
The active material of anode sizing agent of the present invention can adopt a kind of material in the composite oxides of lithium and transition metal or the mixture of several materials.The composite oxides of lithium and transition metal can be LiCoO
2, LiMn
2O
4, LiV
3O
8, LiCoNi
1-XO
2(0＜X＜1) etc.The active material ratio is generally 85%～93% in the anode sizing agent.
Anode sizing agent of the present invention has adopted deionized water as solvent, not only can there be inflammable and explosive problem in people's toxigenicity, meets environmental protection requirement, and reduces in the water inorganic salts greatly to the influence of cell voltage.In addition, it has also adopted CMCNa and the PTFE technical scheme of incompatible bonding positive pole powder that matches, thereby has overcome the shortcoming of the slurry coating performance difference that simple employing PTFE makes, and has increased the stability of anode sizing agent, makes slurry have good coating performance.
Three of purpose of the present invention provides a kind of lithium battery and manufacture method thereof.
Lithium battery of the present invention, the anode pole piece that is adopted are to prepare with above-mentioned anode sizing agent.The collector that this lithium battery adopts is preferably 10～30um high-purity aluminum foil.For example anodal specific discharge capacity parameter of lithium battery Specifeca tion speeification of the present invention and battery capacity parameters etc. all are better than existing lithium battery.
Lithium battery of the present invention can adopt following method manufacturing, and this method has comprised following step:
(1) aqueous solution of preparation cellulose ethers material;
(2) emulsion of adding polytetrafluoroethylene in the aqueous solution of the cellulose ethers material that step (1) obtains, forming viscosity is the adhesive of 1500-10000 centipoise;
(3) progressively add active material powder and conductive agent powder in the adhesive that step (2) obtains, stir, forming viscosity is the anode sizing agent of 2500～15000 centipoises;
(4) anode sizing agent with gained in the step (3) be coated with, roll-in, drying, make the anode pole piece of lithium battery;
(5) utilize that resulting anode pole piece carries out the assembling of lithium battery in the step (4).
In step (1), the aqueous solution of preparation CMCNa preferably adopts the deionized water of conductivity less than 3uS/cm.Though CMCNa is soluble in water, because it dissolves in water rapidly, and form full-bodied gel layer easily and stop moisture further to infiltrate, thereby its swelling property is not satisfactory.In order to make CMCNa even dispersion and fully dissolving in water, preferably dissolve CMCNa 40-70 ℃ water bath with thermostatic control.
In step (2), the concentration of the emulsion of polytetrafluoroethylene is preferably 40%-60%.
In step (3), when in adhesive, adding active material powder and conductive agent powder, need active material powder and conductive agent powder be evenly dispersed in the adhesive adhesive, active material powder and conductive agent powder mixing.The mode of mixing is preferably first high-speed stirred 1～5h, and rotating speed is 500～3500r/nin, vacuum stirring 0.5～4h then, vacuum degree control-0.075～-0.095mPa.After abundant mixing, form anode sizing agent.The viscosity of anode sizing agent preferably is controlled at about 2500～15000 centipoises, and more preferably, viscosity is controlled at about 3000～12000 centipoises.
In order to make the positive electrode powder granule in the slurry moderate, preferably, in step (3) and step (4), increase a step, i.e. the anode sizing agent that step (3) the is obtained step of filtering.Filter the preferred 200 order vacuum filtrations of adopting.
In the step (4), the manufacture method of anode pole piece can adopt conventional method basically: be coated with anode sizing agent on collector, will be coated with collector behind the anode sizing agent then through roll-in, drying, make the anode for lithium battery pole piece.Anode pole piece thickness after roll-in is preferably about 0.135mm.The drying mode of anode pole piece can adopt vacuum drying, preferably, dries more than 12 hours down at 120 ℃.Though the manufacture method of anode pole piece of the present invention can adopt conventional method basically, because solvent of the present invention is water rather than organic solvent, thereby also different in some concrete operations with conventional method.Drying mode can adopt common drying mode---and hot blast impacts.Hot blast can produce by electrically heated mode.The equipment that is adopted in the manufacture process of anode pole piece also can be conventional equipment basically.Because the present invention adopts the adhesive of non-organic solvent, thereby coating apparatus of the present invention does not need as conventional coating apparatus solvent recovering system and explosion protection system to be set.
The present invention prepares the lithium battery method and does not have organic solvent absorption air moisture in the preparation process, cause pole piece caking property to descend, thereby influence the problem of cycle performance of battery, thereby need not to preparation during slurry the humidity of environment carry out strictness control, the equipment that is coated with anode sizing agent does not need to be provided with recovery system and explosion protection system yet.This method has been simplified production process to a certain extent, has reduced the cost of lithium battery anode pole piece.
Below, further specify the present invention in conjunction with the embodiments.
Embodiment
Embodiment 1
LiCoO
2Be 88%, the acetylene black ratio is 5%, and the PTFE ratio is 6%, and the CMC ratio is 1%.At first adopt 40 ℃ of water bath with thermostatic control modes to make CMC solution, 60% the emulsion of PTFE is dissolved in the CMC solution makes binder solution again, the conductance of deionized water is 1uS/cm, and prepared adhesive viscosities is: 2000cp; Positive pole powder is progressively joined again and make slurry in the binder solution, the viscosity of control slurry is 3000cp; Coating, roll-in make anode pole piece then, and pole piece is through 120 ℃ of vacuum drying 12h.
Embodiment 2
LiCoO
2Be 88%, the acetylene black ratio is 5%, and the PTFE ratio is 5%, and the CMC ratio is 2%.At first adopt 50 ℃ of water bath with thermostatic control modes to make CMC solution, 50% the emulsion of PTFE is dissolved in the CMC solution makes binder solution again, the conductance of deionized water is 2uS/cm, and prepared adhesive viscosities is: 3000cp; Positive pole powder is progressively joined again and make slurry in the binder solution, the viscosity of control slurry is 4000cp; Coating, roll-in make anode pole piece then, and pole piece is through 120 ℃ of vacuum drying 13h.
Embodiment 3
LiCoO
2Be 88%, the acetylene black ratio is 5%, and the PTFE ratio is 4%, and the CMC ratio is 3%.At first adopt 60 ℃ of water bath with thermostatic control modes to make CMC solution, 60% the emulsion of PTFE is dissolved in the CMC solution makes binder solution again, the conductance of deionized water is 3uS/cm, and prepared adhesive viscosities is: 3500cp; Positive pole powder is progressively joined again and make slurry in the binder solution, the viscosity of control slurry is 5000cp; Coating, roll-in make anode pole piece then, and pole piece is through 120 ℃ of vacuum drying 14h.
Embodiment 4
LiCoO
2Be 88%, the acetylene black ratio is 5%, and the PTFE ratio is 4%, and the CMC ratio is 3%.At first adopt 60 ℃ of water bath with thermostatic control modes to make CMC solution, 60% the emulsion of PTFE is dissolved in the CMC solution makes binder solution again, the conductance of deionized water is 3uS/cm, and prepared adhesive viscosities is: 5000cp; Positive pole powder is progressively joined again and make slurry in the binder solution, the viscosity of control slurry is 8000cp; Coating, roll-in make anode pole piece then, and pole piece is through 120 ℃ of vacuum drying 14h.
Embodiment 5
LiCoO
2Be 88%, the acetylene black ratio is 5%, and the PTFE ratio is 4%, and the CMC ratio is 3%.At first adopt 60 ℃ of water bath with thermostatic control modes to make CMC solution, 60% the emulsion of PTFE is dissolved in the CMC solution makes binder solution again, the conductance of deionized water is 3uS/cm, and prepared adhesive viscosities is: 8000cp; Positive pole powder is progressively joined again and make slurry in the binder solution, the viscosity of control slurry is 12000cp; Coating, roll-in make anode pole piece then, and pole piece is through 120 ℃ of vacuum drying 14h.
The anode pole piece that embodiment 1-5 is made, the cathode pole piece that graphite material makes, and volume ratio is 1: 1: 1 ethylene carbonate, dimethyl carbonate, the LiPF of diethyl carbonate
6The electrolyte of solution composition is assembled into lithium ion battery.Battery discharges and recharges between 3.00v～4.20v, and the current density when discharging and recharging is 2.7mA/cm
2, the Specifeca tion speeification of measured lithium battery sees Table 1.
The comparison of the Specifeca tion speeification of table 1 lithium battery of the present invention and existing lithium battery
| The lithium battery product | Anodal specific discharge capacity (mAh/g) | Battery capacity (mAh) |
| The lithium battery that embodiment 1 makes | 139 | 609 |
| The lithium battery that embodiment 2 makes | 140 | 613 |
| The lithium battery that embodiment 3 makes | 140 | 613 |
| The lithium battery that embodiment 4 makes | 139 | 615 |
| The lithium battery that embodiment 5 makes | 140 | 615 |
| The lithium battery that prior art is made | 137 | 600 |
Claims (10)
1, a kind ofly prepare the adhesive that lithium battery anode is used, this adhesive contains polytetrafluoroethylene and water, and its viscosity is characterized in that between the 1500-10000 centipoise, also contains one or more cellulose ethers materials in the described adhesive.
2, adhesive as claimed in claim 1 is characterized in that, described cellulose ethers material is selected from hydroxyethylcellulose, methylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose and/or sodium carboxymethylcellulose.
3, adhesive as claimed in claim 1 is characterized in that, described cellulose ethers material is a sodium carboxymethylcellulose.
As the described adhesive of one of claim 1-3, it is characterized in that 4, in described adhesive, the weight ratio of polytetrafluoroethylene and cellulose ethers material is 1-6: 1.
5, adhesive as claimed in claim 4 is characterized in that, used water is deionized water in the described adhesive, and its conductivity is less than 3 μ S/cm.
6, a kind ofly prepare the anode sizing agent that lithium battery anode is used, this anode sizing agent comprises active material, conductive agent and adhesive, described active material is to be selected from a kind of material in lithium and the formed composite oxides of transition metal or the mixture of several materials, described conductive agent is to be selected from a kind of material in acetylene black, crystalline flake graphite, carbon black, the carbon fiber or the mixture of several materials, it is characterized in that described adhesive is to be selected from the adhesive described in one of claim 1-5.
7, anode sizing agent as claimed in claim 6, it is characterized in that, calculate by weight percentage, described conductive agent accounts for 3%～10% of described anode sizing agent total amount, described active material accounts for described anode sizing agent total amount 85%～93%, described polytetrafluoroethylene accounts for described anode sizing agent total amount 3%～7%, and described cellulose ethers material accounts for described anode sizing agent total amount 1%～3%, and surplus is a water.
8, anode sizing agent as claimed in claim 6 is characterized in that, the viscosity of described anode sizing agent is 2500～15000 centipoises, is preferably 3000～12000 centipoises.
9, a kind of lithium battery, the anode pole piece of this lithium battery are to adopt as the described anode sizing agent preparation of one of claim 6～8.
10, a kind of method for preparing lithium battery, this method may further comprise the steps:
(1) aqueous solution of preparation cellulose ethers material;
(2) emulsion of adding polytetrafluoroethylene in the aqueous solution of the cellulose ethers material that step (1) obtains, forming viscosity is the adhesive of 1500-10000 centipoise;
(3) progressively add active material powder and conductive agent powder in the adhesive that step (2) obtains, stir, forming viscosity is the anode sizing agent of 2500～15000 centipoises;
(4) anode sizing agent with gained in the step (3) be coated with, roll-in, drying, make the anode pole piece of lithium battery;
(5) utilize that resulting anode pole piece carries out the assembling of lithium battery in the step (4).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410050866XA CN100352087C (en) | 2004-07-29 | 2004-07-29 | Adhesion agent of anode, pulp for anode obtained, lithium battery ,and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410050866XA CN100352087C (en) | 2004-07-29 | 2004-07-29 | Adhesion agent of anode, pulp for anode obtained, lithium battery ,and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1728427A true CN1728427A (en) | 2006-02-01 |
| CN100352087C CN100352087C (en) | 2007-11-28 |
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|---|---|---|---|
| CNB200410050866XA Expired - Fee Related CN100352087C (en) | 2004-07-29 | 2004-07-29 | Adhesion agent of anode, pulp for anode obtained, lithium battery ,and preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010115361A1 (en) * | 2009-04-09 | 2010-10-14 | Byd Company Limited | Battery electrode plate, preparation method thereof and secondary battery with the same |
| WO2010124560A1 (en) * | 2009-04-30 | 2010-11-04 | Byd Company Limited | Method of preparing an electrode plate and method of manufacturing a lithium-ion battery having the electrode plate |
| CN102610797A (en) * | 2011-12-16 | 2012-07-25 | 北京联飞翔科技股份有限公司 | Manufacturing method of lithium iron phosphate anode |
| CN101937983B (en) * | 2009-06-29 | 2012-12-12 | 上海比亚迪有限公司 | Lithium ion battery negative slurry and lithium ion battery |
| CN106384830A (en) * | 2016-12-06 | 2017-02-08 | 庄爱芹 | Adhesive used for electrode of lithium battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247388A (en) * | 1998-09-10 | 2000-03-15 | 中国科学院物理研究所 | Secondary lithium battery |
| JP3654005B2 (en) * | 1998-09-18 | 2005-06-02 | 新神戸電機株式会社 | Method for producing positive electrode plate for lithium ion secondary battery |
| CN1190858C (en) * | 2000-04-12 | 2005-02-23 | 比亚迪股份有限公司 | Adhered Ni electrode and its making method |
| JP3692965B2 (en) * | 2000-05-15 | 2005-09-07 | 株式会社デンソー | Lithium secondary battery and method for producing positive electrode thereof |
| CN1142611C (en) * | 2001-11-16 | 2004-03-17 | 西安交通大学 | Intraconnected Ni-H2 power accumulator with low inner voltage and high output voltage and its prepn |
-
2004
- 2004-07-29 CN CNB200410050866XA patent/CN100352087C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010115361A1 (en) * | 2009-04-09 | 2010-10-14 | Byd Company Limited | Battery electrode plate, preparation method thereof and secondary battery with the same |
| WO2010124560A1 (en) * | 2009-04-30 | 2010-11-04 | Byd Company Limited | Method of preparing an electrode plate and method of manufacturing a lithium-ion battery having the electrode plate |
| CN101937983B (en) * | 2009-06-29 | 2012-12-12 | 上海比亚迪有限公司 | Lithium ion battery negative slurry and lithium ion battery |
| CN102610797A (en) * | 2011-12-16 | 2012-07-25 | 北京联飞翔科技股份有限公司 | Manufacturing method of lithium iron phosphate anode |
| CN102610797B (en) * | 2011-12-16 | 2015-01-28 | 北京鼎能开源电池科技股份有限公司 | Manufacturing method of lithium iron phosphate anode |
| CN106384830A (en) * | 2016-12-06 | 2017-02-08 | 庄爱芹 | Adhesive used for electrode of lithium battery |
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| Publication number | Publication date |
|---|---|
| CN100352087C (en) | 2007-11-28 |
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