CN101752545A - Electrode of lithium battery, preparation method of electrode and lithium battery adopting electrode - Google Patents
Electrode of lithium battery, preparation method of electrode and lithium battery adopting electrode Download PDFInfo
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- CN101752545A CN101752545A CN200810227797A CN200810227797A CN101752545A CN 101752545 A CN101752545 A CN 101752545A CN 200810227797 A CN200810227797 A CN 200810227797A CN 200810227797 A CN200810227797 A CN 200810227797A CN 101752545 A CN101752545 A CN 101752545A
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- lithium ion
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- ion battery
- conductive agent
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052744 lithium Inorganic materials 0.000 title abstract description 13
- 239000006258 conductive agent Substances 0.000 claims abstract description 87
- 239000004094 surface-active agent Substances 0.000 claims abstract description 51
- 239000007772 electrode material Substances 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 230000008859 change Effects 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 70
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 63
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 150000002466 imines Chemical class 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005486 organic electrolyte Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011268 mixed slurry Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000011883 electrode binding agent Substances 0.000 claims description 4
- 239000011162 core material Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 3
- 238000004513 sizing Methods 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 239000011149 active material Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000009826 distribution Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012876 topography Methods 0.000 description 6
- 229910015645 LiMn Inorganic materials 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 101100464782 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CMP2 gene Proteins 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an electrode of a lithium battery, a preparation method of the electrode and the lithium battery adopting the electrode. The electrode of the lithium battery comprises a current collector and an electrode material coated on the current collector, wherein the electrode material comprises an electrode active substance, a conductive agent and an adhesive; the electrode material further comprises a surface active agent, and the surface active agent is made of the substance that can change the surface characteristic of the conductive agent. The preparation method includes: first, the conductive agent, the surface active agent and a solvent are mixed and stirred into uniform conductive liquid; second, a mixed sizing agent of the electrode active substance, the adhesive and the conductive liquid is coated on the current collector, and is dried, rolled and cut to form the electrode of the lithium battery. The surface active agent is added to the sizing agent, which reduces conglobation of the conductive agent with high-ratio area, thereby not only reducing the using quantity of the conductive agent and increasing the specific energy of the battery, but also ensuring uniform dispersion of the conductive agent in a pole piece, reducing non-uniform polarization of the battery and avoiding over-charging/discharging of partial active substance. Moreover, the service life of the battery is obviously improved.
Description
Technical field
The invention belongs to the secondary cell field, particularly a kind of lithium ion battery is used electrode and preparation method thereof and is adopted the lithium ion battery of this electrode.
Background technology
The positive active material of lithium rechargeable battery generally adopts transition metal oxide, and its powder resistance is big, poorly conductive.In order to improve the electronic conduction ability of electrode, good electron conduction network must formed between the active material particle and between active material particle and the collector.Usually, reach this purpose by adding carbon black or graphite as conductive agent.Negative electrode active material is a material with carbon element, though this class material with carbon element generally all has conductivity preferably, but in repeatedly discharging and recharging, the expansion of material with carbon element is shunk, and intergranular contact is reduced, and the gap increases, even some breaks away from collector, become dead active material, no longer participate in electrode reaction, keep negative material stable in the cyclic process so also need to add conductive agent.
The conductive agent that generally adopts in the lithium ion battery is the carbon class material with high specific surface area at present, contact with collision between the particle in the hole of staying active material as the graphite and the hydrocarbon black powder of electric conducting material and by particle and form conductive network, thisly cross some contact and the conductive capability of the electron propagation ducts that forms only depends on the collision probability between the particle, and how many this collision probabilities is directly proportional with the quantity of particle by the graininess conductor dbus.Therefore in the prior art, the conductivity that increase electrode has only the method by using a large amount of conductive agents to realize.Because conductive agent, as graphite powder, the carbon black equigranular is little, specific surface is big, in the battery production process, ubiquity a kind of more serious technical problem, promptly containing electrode active material, in the preparation process of the slurry of a large amount of conductive agents and adhesive and solvent, conductive agent with higher specific area is very easily reunited, the reunion of conductive agent brings very big difficulty not only for the dispersion of slurry, and directly cause the inconsistency of pole piece inner conductive agent distribution, the inhomogeneous dispersion of conductive agent makes battery part active material in charge and discharge process overcharge or crosses and put, finally causes battery performance to be decayed fast.
Summary of the invention
The objective of the invention is to solve the problem of the lithium ion battery of prior art existence, the extended-life lithium ion battery of good lithium ion cell electrode of a kind of cycle performance and preparation method thereof and this electrode of employing is provided with conductive agent reunion, cycle performance of battery difference.
In order to realize the foregoing invention purpose, the present invention takes following technical proposals:
Lithium ion cell electrode provided by the invention comprises collector and coats electrode material on the collector, described electrode material contains electrode active material, conductive agent and adhesive, wherein, this electrode material also contains a kind of surfactant, and described surfactant is selected from the material that can change the conductive agent surface characteristic.
Lithium ion cell electrode provided by the invention is a lithium ion battery with anodal and lithium ion battery negative pole.Be that described electrode for cell is respectively positive electrode for battery, negative electrode battery; With positive electrode for battery, the corresponding electrode active material of negative electrode battery be respectively positive active material, negative electrode active material; With positive electrode for battery, the corresponding collector of negative electrode battery be respectively plus plate current-collecting body, negative current collector.Just, lithium ion battery comprises collector and coats electrode material on the plus plate current-collecting body with anodal, described electrode material contains positive active material, conductive agent and adhesive, wherein, this electrode material also contains a kind of surfactant, and described surfactant is selected from the material that can change the conductive agent surface characteristic; Lithium ion battery comprises collector with negative pole and coats electrode material on the negative current collector, described electrode material contains negative electrode active material, conductive agent and adhesive, wherein, this electrode material also contains a kind of surfactant, and described surfactant is selected from the material that can change the conductive agent surface characteristic.
Described surfactant is one or several in polyacrylate, polyurethane, polyvinyl imines and the polyvinyl butyral.The number average molecular weight distribution scope of polyacrylate, polyurethane, polyvinyl imines and polyvinyl butyral is 500～500000, and wherein preferable range 4000～40000, and most preferred range is 8000～20000.
Weight with described conductive agent is benchmark, and the content of described surfactant is the 1-20 weight % of conductive agent weight.That is to say that in lithium ion cell electrode, perhaps use in the negative pole with positive pole or lithium ion battery at lithium ion battery, the content of described surfactant is the 1-20 weight % of conductive agent weight.
Lithium ion battery provided by the invention comprises that with the preparation method of electrode at first conductive agent, solvent and surfactant being mixed stirring makes uniform conductive liquid, secondly the mixed slurry with electrode active material, binding agent and conductive liquid is coated on the collector, and the lithium ion battery electrode is made in drying, roll extrusion and cutting moulding.
In more detail, the present invention provides lithium ion battery is used negative pole with anodal and lithium ion battery preparation method:
The anodal preparation method of a kind of lithium ion battery, comprise at first conductive agent, solvent and surfactant being mixed to stir and make uniform conductive liquid, secondly the mixed slurry with positive active material, binding agent and conductive liquid is coated on the plus plate current-collecting body, and drying, roll extrusion and cutting moulding are made lithium ion battery with anodal.
A kind of lithium ion battery preparation method of negative pole, comprise at first conductive agent, solvent and surfactant being mixed to stir and make uniform conductive liquid, secondly the mixed slurry with negative electrode active material, binding agent and conductive liquid is coated on the negative current collector, and the lithium ion battery negative pole is made in drying, roll extrusion and cutting moulding.
With among the preparation method of electrode, described surfactant is one or several in polyacrylate, polyurethane, polyvinyl imines and the polyvinyl butyral at above-mentioned lithium ion battery.The number average molecular weight distribution scope of described surfactant is 500～500000, and wherein preferable range 4000～40000, and most preferred range is 8000～20000.
With among the preparation method of electrode, is benchmark with the weight of described conductive agent at above-mentioned lithium ion battery, and the content of described surfactant is the 1-20 weight % of conductive agent weight.Promptly use among the preparation method of negative pole with anodal preparation method or at lithium ion battery at lithium ion battery, the content of described surfactant is the 1-20 weight % of conductive agent weight.
Use among the preparation method of electrode at above-mentioned lithium ion battery, described solvent is selected from N-methyl pyrrolidone (NMP), N, one or more in dinethylformamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO) and the oxolane (THF); Weight with described electrode material is benchmark, and the consumption of described solvent is 50～120 weight % of the weight of electrode material.Promptly use among the preparation method of negative pole with anodal preparation method or at lithium ion battery at lithium ion battery, the consumption of described solvent is 50～120 weight % of the weight of electrode material.
With among the preparation method of electrode, is benchmark with the weight of described electrode material at above-mentioned lithium ion battery, and the consumption of described solvent is preferably 80～100 weight % of the weight of electrode material.Promptly use among the preparation method of negative pole with anodal preparation method or at lithium ion battery at lithium ion battery, the consumption of described solvent all is preferably 80～100 weight % of the weight of electrode material.
Lithium ion battery provided by the invention comprises volume core, organic electrolyte and metal shell, described volume core and organic electrolyte are sealed in the metal shell, described volume core comprises electrode for cell of the present invention and barrier film, described electrode for cell comprises collector and is coated in electrode material on the collector, described electrode material contains electrode active material, conductive agent, binding agent and surfactant, and described surfactant is selected from the material that can change the conductive agent surface characteristic.Electrode for cell of the present invention is respectively positive electrode for battery, negative electrode battery.That is to say, described volume core comprises positive electrode for battery of the present invention and negative electrode battery and barrier film, described positive electrode for battery comprises plus plate current-collecting body and is coated in electrode material on the plus plate current-collecting body, described electrode material contains positive active material, conductive agent, binding agent and surfactant, and described surfactant is selected from the material that can change the conductive agent surface characteristic; Described negative electrode battery comprises negative current collector and is coated in electrode material on the negative current collector, described electrode material contains negative electrode active material, conductive agent, binding agent and surfactant, and described surfactant is selected from the material that can change the conductive agent surface characteristic.
According to the present invention, in slurry, add surfactant, reduced the reunion of high specific area conductive agent, not only reduced the consumption of conductive agent, improve the battery specific energy, and guaranteed the even dispersion of conductive agent in pole piece, reduced the inhomogeneous polarization of battery, avoided the super-charge super-discharge of part active material, the life-span of battery be improved significantly.
Description of drawings
Fig. 1 is the photo of four kinds of conductive liquid, and wherein, A1, A2, A3, A4 are respectively and adopt electron microscope to observe the photo of the distribution of conductive agent among conductive liquid A1, A2, A3, the A4.
Fig. 2 is the photo of two kinds of positive plates, and wherein, B1 observes the photo of the surface topography of positive plate B1 for adopting electronic scanner microscope (SEM); B1-D observes the photo of the surface topography of positive plate B1-D for adopting electronic scanner microscope (SEM).
Fig. 3 is the photo of the distribution of two kinds of conductive agents, and wherein, A1-D, A2-D are respectively and adopt electron microscope to observe the photo of the distribution of conductive agent among A1-D and the A2-D.
Embodiment
According to the present invention, under the preferable case, described surfactant is preferably one or several in the polyacrylate that can dissolve, polyurethane, polyvinyl imines (PEI), polyvinyl butyral (PVB) the class material in organic solvents such as DMF, NMP, above-mentioned surfactant is available commercially, as the polyurethanes dispersant KD-1 of Uniqema company production.
According to the present invention, as long as add the surface characteristic that described surfactant just can change conductive agent, reduce the reunion of conductive agent, help the even dispersion of conductive agent in pole piece.Under the preferable case, be benchmark with the weight of described conductive agent, the content of described surfactant is the 1-20 weight % of conductive agent weight, is preferably 5-10 weight %.
According to the electrode of lithium ion battery provided by the invention, comprise positive electrode for battery and negative pole.Described positive active material is not particularly limited, and can be selected from the active material of the embedded removal lithium embedded ion of this area routine.Comprise stratiform cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2) or spinel lithium manganate (LiMn
2O
4), or other can the embedding lithium takes off the active material of lithium.Described negative electrode active material is one or several in Delanium, native graphite, agraphitic carbon, the lithium titanate.
Described conductive agent can be selected from the electrodes conduct agent of this area routine, at least a such as in acetylene black, conductive carbon fibre, conductive carbon black and the electrically conductive graphite.In lithium ion cell electrode, electrode active material: conductive agent: the weight ratio of bonding agent is 77-94: 1-15: 4.5-8; With in the positive pole, positive active material: conductive agent: the weight ratio of bonding agent is 77-94: 1-15: 4.5-8 at lithium ion battery; With in the negative pole, negative electrode active material: conductive agent: the weight ratio of bonding agent is 77-94: 1-15: 4.5-8 at lithium ion battery.
The preparation method of slurry who contains electrode active material, conductive agent and adhesive and solvent is mixed and made into slurry with electrode active material, binding agent and conductive liquid then at first conductive agent, surfactant and solvent fully being hybridly prepared into conductive liquid.Wherein said solvent can be selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) one or more.In general, be benchmark with the weight of described electrode material, the consumption of described solvent is 50-120 weight %, is preferably 80-100 weight %.
Collector can be collector conventional in the lithium ion battery, uses aluminium foil as plus plate current-collecting body in specific embodiments of the present invention, and Copper Foil is as negative current collector.
According to lithium ion battery provided by the present invention, its positive pole, barrier film, negative pole stack the coiling core successively, and described volume core and organic electrolyte are sealed in the metal shell together.Described barrier film is selected from various barrier films used in the lithium ion battery, as microporous polyolefin film.Described organic electrolyte is the mixed solution of organic solvent and inorganic lithium salt.
Embodiment 1
This embodiment illustrates lithium ion battery provided by the invention and electrode and their preparation method.
1) anodal preparation: with 110g gas-phase growth of carbon fibre (VGCF) and 11g surfactant kd-1 dry powder blend, add 1000g N-methyl pyrrolidone (NMP) then and stir into uniform conductive agent suspending liquid A 1, at last with conductive agent suspension and 1000g LiMn2O4 (LiMn
2O
4) and the binding agent of 60g mix, adopt the mode of vacuum stirring to prepare the electrode slurry of uniformity.This slurry is coated on the aluminium foil, oven dry, roll extrusion then, is cut to long 1500mm, the positive plate B1 of wide 300mm, wherein active material LiMn
2O
4Content be 90g.
2) negative pole preparation: with 56g gas-phase growth of carbon fibre (VGCF) and 5g surfactant kd-1 dry powder blend, add 1000g N-methyl pyrrolidone (NMP) then and stir into uniform conductive agent suspending liquid A 2, binding agent with conductive agent suspension and 1000g Delanium CMS and 56g mixes at last, and the mode of employing vacuum stirring is prepared the electrode slurry of uniformity.This slurry is coated on the Copper Foil, oven dry, roll extrusion then, is cut to long 1520mm, the negative plate B1 of wide 310mm, wherein the content of active material CMS is 33g.
3) preparation of battery: positive plate, barrier film, negative plate stacked successively be wound into core, will roll up core and put into metal-back, fluid injection then, seal, change into and be 8Ah lithium ion battery C1.
Comparative Examples 1:
This Comparative Examples explanation does not contain electrode, battery of surfactant and preparation method thereof:
According to embodiment 1 preparation electrode and battery, different is not contain surfactant in the conductive liquid, and the amount of other compositions and embodiment 1 are identical, obtain anodal conductive liquid A1-D, negative pole conductive liquid A2-D and positive plate B1-D, battery C1-D.
Embodiment 2
1) anodal preparation: with 56g conductive carbon black (SP) and 11g surfactant polyvinyl butyral (PVB) dry powder blend, add 1000g N-methyl pyrrolidone (NMP) then and stir into uniform conductive agent suspending liquid A 3, at last with conductive agent suspension and 1000g LiMn2O4 (LiMn
2O
4) and the binding agent of 56g mix, adopt the mode of vacuum stirring to prepare the electrode slurry of uniformity.This slurry is coated on the aluminium foil, oven dry, roll extrusion then, is cut to long 1000mm, the positive plate of wide 400mm, wherein active material LiMn
2O
4Content be 90g.
2) negative pole preparation: with 25g conductive carbon black (SP) and 4g surfactant polyvinyl butyral (PVB) dry powder blend, add 1000g N-methyl pyrrolidone (NMP) then and stir into uniform conductive agent suspending liquid A 4, binding agent with conductive agent suspension and 1000g Delanium CMP2 and 50g mixes at last, and the mode of employing vacuum stirring is prepared the electrode slurry of uniformity.This slurry is coated on the Copper Foil, oven dry, roll extrusion then, is cut to long 1020mm, the negative plate of wide 410mm, wherein the content of active material CMP2 is 30g.
3) preparation of battery: positive plate, barrier film, negative plate stacked successively be wound into core, will roll up core and put into metal-back, fluid injection then, seal, change into and be 7Ah lithium ion battery C2.
Embodiment 3
1) anodal preparation: 110g gas-phase growth of carbon fibre (VGCF) is mixed with the 12g surfactant, add 1000gN then, dinethylformamide (DMF) stirs into uniform conductive agent suspension; All the other are with embodiment 1.
2) negative pole preparation: 56g gas-phase growth of carbon fibre (VGCF) is mixed with 6g surfactant polyvinyl imines (PEI), add 1000g N then, dinethylformamide (DMF) stirs into uniform conductive agent suspension; All the other are with embodiment 1.
3) preparation of battery: positive plate, barrier film, negative plate stacked successively be wound into core, will roll up core and put into metal-back, fluid injection then, seal, change into and be 8Ah lithium ion battery C3.
Embodiment 4
1) anodal preparation: 56g conductive carbon black (SP) is mixed with 11g surfactant polyacrylate, add 1000g N-methyl pyrrolidone (NMP) then and stir into uniform conductive agent suspension; All the other are with embodiment 2.
2) negative pole preparation: 25g conductive carbon black (SP) is mixed with 4g surfactant polyacrylate, add 1000g N-methyl pyrrolidone (NMP) then and stir into uniform conductive agent suspension; All the other are with embodiment 2.
3) preparation of battery: positive plate, barrier film, negative plate stacked successively be wound into core, will roll up core and put into metal-back, fluid injection then, seal, change into and be 7Ah lithium ion battery C4.
Embodiment 5-9
The following example 5～9 is measured the distribution of conductive agent among conductive liquid A1, A2, A3, the A4 and the surface topography of positive plate B1 respectively, the distribution of conductive agent adopts electron microscope to observe, and the surface topography of positive plate adopts electronic scanner microscope (SEM) to observe.Fig. 1 is the photo of four kinds of conductive liquid, and wherein, A1, A2, A3, A4 are respectively and adopt electron microscope to observe the photo of the distribution of conductive agent among conductive liquid A1, A2, A3, the A4.Fig. 2 is the photo of two kinds of positive plates, and wherein, B1 observes the photo of the surface topography of positive plate B1 for adopting electronic scanner microscope (SEM).
Comparative Examples 2-4
Following Comparative Examples is measured in the Comparative Examples 1 among the conductive liquid A1-D and A2-D the distribution of conductive agent and the SEM of positive plate B1-D respectively.The same electron microscope that adopts is observed the distribution of conductive agent in conductive liquid, adopts the pattern of SEM observation positive plate.Fig. 3 is the photo of the distribution of two kinds of conductive agents, and wherein, A1-D, A2-D are respectively and adopt electron microscope to observe the photo of the distribution of conductive agent among A1-D and the A2-D.Fig. 2 is the photo of two kinds of positive plates, and wherein, B1-D observes the photo of the surface topography of positive plate B1-D for adopting electronic scanner microscope (SEM).
Clearly reflected among the figure, add after the surfactant, the agglomeration of conductive agent obviously reduces, adopt among the positive plate B1 that the A1 conductive liquid prepares conductive agent to distribute uniformly or be coated on around the active material, and conductive agent is reunited in a large number around the part active material among the positive plate B1-D that employing A1-D conductive liquid is prepared, and does not have the distribution of conductive agent in the pole piece around the active material of many places.
Embodiment 10-13
The following example is measured the cycle performance of battery C1, C2, C3, C4 among the embodiment 1,2,3,4 respectively.
Loop test mode: under the room temperature condition, battery is changeed constant voltage with 1C electric current constant current charge respectively to 4.2V, when electric current drop to initial current 10% after stop the charging, battery left standstill 30 minutes, then with 1C electric current constant-current discharge to 3.2V, shelved 15 minutes.Repeat above step 100 time.Test result sees Table 1.
Table 1
| The embodiment numbering | 100 all capability retentions circulate |
| Embodiment 10 | 94% (cycle performance of embodiment 1 battery C1) |
| The embodiment numbering | 100 all capability retentions circulate |
| Embodiment 11 | 95% (cycle performances of embodiment 2 battery C2) |
| Comparative Examples 5 | 85% (cycle performance of C1-D battery in the Comparative Examples 1) |
| Embodiment 12 | 94% (cycle performances of embodiment 3 battery C3) |
| Embodiment 13 | 93% (cycle performances of embodiment 4 battery C4) |
Comparative Examples 5
The following example is measured the cycle performance of C1-D battery in the Comparative Examples 1 respectively.Method of testing is same as embodiment 10-14.Test result is as shown in table 1.
Test result from table 1 finds out, lithium ion battery cycle performance provided by the invention be improved significantly.
Claims (13)
1. lithium ion battery electrode, it is characterized in that: this lithium ion cell electrode comprises collector and coats electrode material on the collector, described electrode material contains electrode active material, conductive agent and adhesive, wherein, this electrode material also contains a kind of surfactant, and described surfactant is selected from the material that can change the conductive agent surface characteristic.
2. lithium ion battery electrode according to claim 1 is characterized in that: described electrode for cell is respectively positive electrode for battery, negative electrode battery; With positive electrode for battery, the corresponding electrode active material of negative electrode battery be respectively positive active material, negative electrode active material; With positive electrode for battery, the corresponding collector of negative electrode battery be respectively plus plate current-collecting body, negative current collector.
3. lithium ion battery electrode according to claim 1 and 2 is characterized in that: described surfactant is one or several in polyacrylate, polyurethane, polyvinyl imines and the polyvinyl butyral.
4. lithium ion battery electrode according to claim 1 and 2 is characterized in that: the weight with described conductive agent is benchmark, and the content of described surfactant is the 1-20 weight % of conductive agent weight.
5. lithium ion battery electrode according to claim 3 is characterized in that: the weight with described conductive agent is benchmark, and the content of described surfactant is the 1-20 weight % of conductive agent weight.
6. one kind prepares the method that the described lithium ion battery of claim 1 is used electrode, it is characterized in that: this method comprises the steps: at first conductive agent, surfactant and solvent to be stirred to make uniform conductive liquid; Secondly the mixed slurry with electrode active material, binding agent and conductive liquid is coated on the collector, and the lithium ion battery electrode is made in drying, roll extrusion and cutting moulding.
7. the lithium ion battery according to claim 6 preparation method of electrode, it is characterized in that: the electrode active material that is adopted is respectively positive active material, negative electrode active material, and be coated in respectively on positive pole, the negative current collector with the mixed slurry of binding agent and conductive liquid respectively, dry, roll extrusion and cutting moulding are made lithium ion battery respectively with positive pole, lithium ion battery negative pole.
8. the lithium ion battery according to claim 6 preparation method of electrode, it is characterized in that: described surfactant is one or several in polyacrylate, polyurethane, polyvinyl imines and the polyvinyl butyral.
9. the lithium ion battery according to claim 8 preparation method of electrode, it is characterized in that: the weight with described conductive agent is benchmark, the content of described surfactant is the 1-20 weight % of conductive agent weight.
10. according to claim 6 or 7 described lithium ion batteries preparation method with electrodes, it is characterized in that: described solvent is selected from N-methyl pyrrolidone (NMP), N, one or more in dinethylformamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO) and the oxolane (THF); Weight with described electrode material is benchmark, and the consumption of described solvent is 50～120 weight % of the weight of electrode material.
11. the lithium ion battery according to claim 10 preparation method of electrode, it is characterized in that: the weight with described electrode material is benchmark, and the consumption of described solvent is 80～100 weight % of the weight of electrode material.
12. lithium ion battery that the described lithium ion battery of claim 1 is installed with electrode, it is characterized in that: this lithium ion battery comprises volume core, organic electrolyte and metal shell, described volume core and organic electrolyte are sealed in the metal shell, and described volume core comprises the electrode and the barrier film of the described lithium ion battery of claim 1.
13. the lithium ion battery according to claim 12 lithium ion battery of electrode, it is characterized in that: described electrode for cell is respectively positive electrode for battery, negative electrode battery; With positive electrode for battery, the corresponding electrode active material of negative electrode battery be respectively positive active material, negative electrode active material; With positive electrode for battery, the corresponding collector of negative electrode battery be respectively plus plate current-collecting body, negative current collector.
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| CN102074678A (en) * | 2010-12-24 | 2011-05-25 | 上海中兴派能能源科技有限公司 | High-volume-density lithium ion battery anode, manufacturing method and high-volume lithium ion battery |
| CN102170018A (en) * | 2011-03-31 | 2011-08-31 | 东莞新能源科技有限公司 | Lithium-ion secondary battery |
| CN102303007A (en) * | 2011-09-02 | 2012-01-04 | 深圳市格瑞普电池有限公司 | Method for coating electrode plate for lithium ion battery, electrode plate for lithium ion battery, and lithium ion battery |
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| CN103682305B (en) * | 2013-10-15 | 2016-01-20 | 深圳金山电池有限公司 | High capacity lithium ion battery anode sizing agent and preparation method thereof |
| CN103872306A (en) * | 2014-03-24 | 2014-06-18 | 四川剑兴锂电池有限公司 | Preparation method of lithium titanate negative electrode slurry |
| CN113358428A (en) * | 2021-04-26 | 2021-09-07 | 万向一二三股份公司 | Lithium battery pole piece processing method |
| CN116264267A (en) * | 2021-12-14 | 2023-06-16 | 三星Sdi株式会社 | Electrode, lithium battery including the same, and method of manufacturing the same |
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Application publication date: 20100623 |