CN117810455A - Graphite negative electrode material with strong cohesiveness and preparation method thereof - Google Patents
Graphite negative electrode material with strong cohesiveness and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000010439 graphite Substances 0.000 title claims abstract description 103
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 103
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000853 adhesive Substances 0.000 claims abstract description 23
- 230000001070 adhesive effect Effects 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 95
- 238000006243 chemical reaction Methods 0.000 claims description 62
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 37
- 239000010405 anode material Substances 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 30
- 229940126062 Compound A Drugs 0.000 claims description 28
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- BOBATFKNMFWLFG-UHFFFAOYSA-N 2-amino-2-cyano-n-methylacetamide Chemical compound CNC(=O)C(N)C#N BOBATFKNMFWLFG-UHFFFAOYSA-N 0.000 claims description 20
- JJUBFBTUBACDHW-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JJUBFBTUBACDHW-UHFFFAOYSA-N 0.000 claims description 20
- PMOWTIHVNWZYFI-UHFFFAOYSA-N o-Coumaric acid Natural products OC(=O)C=CC1=CC=CC=C1O PMOWTIHVNWZYFI-UHFFFAOYSA-N 0.000 claims description 20
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011267 electrode slurry Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000006257 cathode slurry Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007770 graphite material Substances 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a graphite negative electrode material with strong cohesiveness and a preparation method thereof, wherein the graphite negative electrode material comprises 75-85wt% of graphite, 8-13wt% of binder and 7-12wt% of conductive agent according to weight percentage; the side chain of the adhesive contains phenolic hydroxyl and amino, and a stable three-dimensional network structure formed by self-crosslinking can coat graphite, so that the volume expansion effect of a graphite material after multiple charge and discharge cycles is effectively limited, the bonding effect between a graphite negative electrode material and a current collector is improved, and the adhesive can be crosslinked with active groups on the surface of the graphite to fix the graphite, further inhibit the graphite from peeling off due to volume expansion, and improve the cycling stability of the electrode; the introduction of organic fluorine can form a stable C-F bond, so that the bonding strength of the graphite material can be further improved, the graphite negative electrode material can be better adhered to a current collector in the charge and discharge process, and the cycling stability of the electrode is further improved.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials, and particularly relates to a graphite negative electrode material with strong cohesiveness and a preparation method thereof.
Background
The lithium ion battery consists of different materials, the performance of the battery mainly depends on the positive electrode, the negative electrode, the diaphragm and the electrolyte material, graphite is the most commonly used negative electrode material of the current lithium ion battery, but after a plurality of charge and discharge cycles, the graphite is easy to peel off due to larger volume change, so that the capacity is attenuated, and the binder plays a role of combining the graphite, the conductive agent and the current collector in the negative electrode material.
The current commercial lithium ion battery adhesive mainly adopts polyvinylidene fluoride (PVDF), but because the PVDF can obviously expand in an organic solvent, N-methyl pyrrolidone is required to be used as a solvent, acetone is required to be used as a diluent, but the PVDF can obviously expand in the organic solvent, only can provide weak intermolecular acting force, so that the bonding strength between graphite and a current collector is not high, graphite peeling can be caused in the battery charging and discharging process, and the battery cycle stability can be reduced.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a graphite negative electrode material with strong cohesiveness and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the graphite negative electrode material with strong cohesiveness comprises the following raw materials in percentage by weight:
75-85wt% of graphite, 8-13wt% of binder and 7-12wt% of conductive agent;
the preparation of the adhesive comprises the following steps:
step A1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, feeding into a reaction kettle, controlling the stirring speed to be 100-150r/min, heating to 60-75 ℃, reacting for 3-5h, and then drying in an oven at 65-70 ℃ for 3h to obtain a compound A;
further, the dosage ratio of the 2-hydroxy cinnamic acid, the 2-perfluorooctyl ethanol, the stannous oxide and the acetone is 6 to 8.5g:17-23.5g:0.5-1g:70-85mL;
2-hydroxy cinnamic acid and 2-perfluoro octyl ethanol react under the catalysis of stannous oxide, the 2-perfluoro octyl ethanol is grafted to 2-hydroxy cinnamic acid molecules, carbon-carbon double bonds, hydroxyl and fluoro are introduced, and the structural formula of the compound A is shown as follows:
step A2: mixing and feeding the compound A, butenamide, AIBN and DMF into a reaction kettle, controlling the stirring reaction rate to be 200-250r/min, heating to 60-70 ℃, and stirring and reacting for 4-5h to obtain the binder.
Further, the dosage ratio of the compound A, the butenamide, the AIBN and the DMF is 20-25g:3.5-5g:0.2-0.5g:65-80mL;
the compound A and the butenamide are copolymerized under the action of an AIBN initiator, and amino is introduced to obtain the adhesive.
A preparation method of a graphite anode material with strong cohesiveness comprises the following steps:
step S1: mixing graphite, a conductive agent and deionized water, feeding into a stirring tank, controlling the stirring speed to be 200-300r/min, stirring for 0.5h at normal temperature, adding an adhesive, controlling the stirring speed to be 500-700r/min, and stirring for 0.5-1h at normal temperature to obtain graphite cathode slurry;
further, the solid content of the graphite anode slurry was 50%.
Step S2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 300-400r/min, heating to 85-95 ℃, preserving heat for 3-4h, transferring into a vacuum drying oven, controlling the temperature to be 60-70 ℃, and drying for 6-8h to obtain the graphite anode material.
The invention has the beneficial effects that:
the invention discloses a graphite negative electrode material with strong cohesiveness and a preparation method thereof, wherein graphite and a current collector are combined by compounding a self-made binder, so that the cohesiveness of the graphite negative electrode material is improved;
the side chain of the adhesive contains phenolic hydroxyl and amino, a stable three-dimensional network structure formed by self-crosslinking can cover graphite, the network structure can effectively limit the volume expansion effect of a graphite material after multiple charge and discharge cycles, the graphite is restrained from falling off from a current collector due to volume expansion, the bonding effect between a graphite negative electrode material and the current collector is improved, simultaneously, the hydroxyl and amino in the side chain can be crosslinked with active groups on the surface of the graphite to fix the graphite, the graphite is further restrained from falling off due to volume expansion, and the cycle stability of the electrode is improved;
the introduction of organic fluorine can form a stable C-F bond, so that the bonding strength of the graphite material can be further improved, the graphite negative electrode material can be better adhered to a current collector in the charge and discharge process, and the cycling stability of the electrode is further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The implementation process for preparing the graphite anode material with strong cohesiveness in the embodiment is as follows:
1) Preparation of the adhesive
a1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, feeding into a reaction kettle, controlling the stirring speed to be 100r/min, heating to 60 ℃, reacting for 3 hours, and then drying in a drying oven at 65 ℃ for 3 hours to obtain a compound A; in the above reaction, the ratio of the amount of 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone was 6g:17g:0.5g:70mL;
a2: mixing and feeding a compound A, butenamide and AIBN (the azo-diisobutyronitrile of Shanghai Michelson chemical reagent limited company is selected in the embodiment, the model is M26745) and DMF (the N, N-dimethylformamide of Shanghai Michelson chemical reagent limited company is selected in the embodiment, the model is M8657) into a reaction kettle, controlling the stirring reaction rate to be 200r/min, heating to 60 ℃, and stirring and reacting for 4 hours to obtain a binder; in the above reaction, the amount ratio of compound A, butenamide, AIBN and DMF was 20g:3.5g:0.2g:65mL;
2) Preparing a graphite anode material with strong cohesiveness:
s1: mixing 7.5g of graphite, 1.2g of conductive agent (conductive carbon black of Tianjin U.S. chemical engineering Co., ltd. In this example and comparative example) and deionized water, feeding into a stirring tank, stirring at a stirring rate of 200r/min at normal temperature for 0.5h, adding 1.3g of adhesive, stirring at a stirring rate of 500r/min at normal temperature for 0.5h to obtain graphite negative electrode slurry with a solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 300r/min, heating to 85 ℃, preserving heat for 3 hours, transferring into a vacuum drying oven, controlling the temperature to be 60 ℃, and drying for 6 hours to obtain a graphite anode material with strong cohesiveness;
example 2
The implementation process for preparing the graphite anode material with strong cohesiveness in the embodiment is as follows:
1) Preparation of the adhesive
a1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, feeding the mixture into a reaction kettle, controlling the stirring rate to be 150r/min, heating to 70 ℃, and reacting for 5 hours to obtain a compound A; in the above reaction, the ratio of the amount of 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone was 8.5g:23.5g:1g:85mL;
a2: mixing and feeding the compound A, butenamide, AIBN and DMF into a reaction kettle, controlling the stirring reaction rate to be 250r/min, heating to 80 ℃, and stirring and reacting for 5 hours to obtain a binder; in the above reaction, the amount ratio of compound A, butenamide, AIBN and DMF was 25g:5g:0.5g:80mL;
2) Preparing a graphite anode material with strong cohesiveness:
s1: mixing 8.5g of graphite, 0.7g of conductive agent and deionized water, feeding into a stirring tank, controlling the stirring speed to 300r/min, stirring at normal temperature for 0.5h, adding 0.8g of adhesive, controlling the stirring speed to 700r/min, and stirring at normal temperature for 1h to obtain graphite negative electrode slurry with the solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 400r/min, heating to 95 ℃, preserving heat for 4 hours, transferring into a vacuum drying oven, controlling the temperature to be 70 ℃, and drying for 8 hours to obtain a graphite anode material with strong cohesiveness;
example 3
The implementation process for preparing the graphite anode material with strong cohesiveness in the embodiment is as follows:
1) Preparation of the adhesive
a1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, feeding into a reaction kettle, controlling the stirring speed to be 100r/min, heating to 60 ℃, reacting for 3 hours, and then drying in a drying oven at 65 ℃ for 3 hours to obtain a compound A; in the above reaction, the ratio of the amount of 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone was 6g:17g:0.5g:70mL;
a2: mixing and feeding a compound A, butenamide, AIBN and DMF into a reaction kettle, controlling the stirring reaction rate to be 200r/min, heating to 60 ℃, and stirring and reacting for 4 hours to obtain a binder; in the above reaction, the amount ratio of compound A, butenamide, AIBN and DMF was 20g:3.5g:0.2g:65mL;
2) Preparing a graphite anode material with strong cohesiveness:
s1: mixing 8g of graphite, 1g of a conductive agent and deionized water, feeding into a stirring tank, controlling the stirring speed to be 200r/min, stirring for 0.5h at normal temperature, adding 1g of an adhesive, controlling the stirring speed to be 500r/min, and stirring for 1h at normal temperature to obtain graphite negative electrode slurry with the solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 300r/min, heating to 85 ℃, preserving heat for 3 hours, transferring into a vacuum drying oven, controlling the temperature to be 60 ℃, and drying for 6 hours to obtain a graphite anode material with strong cohesiveness;
example 4
The implementation process for preparing the graphite anode material with strong cohesiveness in the embodiment is as follows:
1) Preparation of the adhesive
a1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, feeding into a reaction kettle, controlling the stirring speed to be 120r/min, heating to 65 ℃, stirring for reaction for 4 hours, and then drying in an oven at 70 ℃ for 3 hours to obtain a compound A; in the above reaction, the ratio of the amount of 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone was 8.5g:23.5g:1g:85mL;
a2: mixing and feeding a compound A, butenamide, AIBN and DMF into a reaction kettle, controlling the stirring reaction rate to be 220r/min, heating to 70 ℃, and reacting for 4.5 hours to obtain a binder; in the above reaction, the amount ratio of compound A, butenamide, AIBN and DMF was 25g:5g:0.5g:80mL;
2) Preparing a graphite anode material with strong cohesiveness:
s1: mixing 8.5g of graphite, 0.7g of conductive agent and deionized water, feeding into a stirring tank, controlling the stirring speed to be 250r/min, stirring for 0.5h at normal temperature, adding 0.8g of adhesive, controlling the stirring speed to be 600r/min, and stirring for 1h at normal temperature to obtain graphite negative electrode slurry with the solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 300r/min, heating to 85 ℃, preserving heat for 3.5h, transferring into a vacuum drying oven, controlling the temperature to be 65 ℃, and drying for 6h to obtain a graphite anode material with strong cohesiveness;
example 5
The implementation process for preparing the graphite anode material with strong cohesiveness in the embodiment is as follows:
1) Preparation of the adhesive
a1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, feeding the mixture into a reaction kettle, controlling the stirring speed to be 130r/min, heating to 70 ℃, stirring and reacting for 4.5 hours, and then drying in an oven at 68 ℃ for 3 hours to obtain a compound A; in the above reaction, the ratio of the amount of 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone was 8.5g:23.5g:0.5g:70mL;
a2: mixing and feeding the compound A, butenamide, AIBN and DMF into a reaction kettle, controlling the stirring reaction rate to be 230r/min, heating to 66 ℃, and reacting for 4.5 hours to obtain a binder; in the above reaction, the amount ratio of compound A, butenamide, AIBN and DMF was 25g:5g:0.2g:65mL;
2) Preparing a graphite anode material with strong cohesiveness:
s1: mixing 8.5g of graphite, 0.7g of conductive agent and deionized water, feeding into a stirring tank, controlling the stirring speed to be 280r/min, stirring for 0.5h at normal temperature, adding 0.8g of adhesive, controlling the stirring speed to be 650r/min, and stirring for 1h at normal temperature to obtain graphite negative electrode slurry with the solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 350r/min, heating to 90 ℃, preserving heat for 3.5h, transferring into a vacuum drying oven, controlling the temperature to be 62 ℃, and drying for 6h to obtain a graphite anode material with strong cohesiveness;
example 6
The implementation process for preparing the graphite anode material with strong cohesiveness in the embodiment is as follows:
1) Preparation of the adhesive
a1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, feeding the mixture into a reaction kettle, controlling the stirring rate to be 130r/min, heating to 70 ℃, and stirring and reacting for 4.5 hours to obtain a compound A; in the above reaction, the ratio of the amount of 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone was 7g:20g:0.5g:70mL;
a2: mixing and feeding a compound A, butenamide, AIBN and DMF into a reaction kettle, controlling the stirring reaction rate to be 230r/min, heating to 70 ℃, and reacting for 4.5 hours to obtain a binder; in the above reaction, the amount ratio of compound A, butenamide, AIBN and DMF was 22g:4g:0.2g:65mL;
2) Preparing a graphite anode material with strong cohesiveness:
s1: mixing 8.5g of graphite, 0.7g of conductive agent and deionized water, feeding into a stirring tank, controlling the stirring speed to be 280r/min, stirring for 0.5h at normal temperature, adding 0.8g of adhesive, controlling the stirring speed to be 600r/min, and stirring for 1h at normal temperature to obtain graphite negative electrode slurry with the solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 370r/min, heating to 92 ℃, preserving heat for 3.5h, transferring into a vacuum drying oven, controlling the temperature to be 65 ℃, and drying for 6h to obtain a graphite anode material with strong cohesiveness;
example 7
The implementation process for preparing the graphite anode material with strong cohesiveness in the embodiment is as follows:
1) Preparation of the adhesive
a1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, feeding the mixture into a reaction kettle, controlling the stirring speed to be 130r/min, heating to 70 ℃, and stirring and reacting for 4 hours to obtain a compound A; in the above reaction, the ratio of the amount of 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone was 7.5g:21.5g:0.8g:80mL;
a2: mixing and feeding the compound A, butenamide, AIBN and DMF into a reaction kettle, controlling the stirring reaction rate to be 230r/min, heating to 66 ℃, and reacting for 4.5 hours to obtain a binder; in the above reaction, the amount ratio of compound A, butenamide, AIBN and DMF was 22.5g:4g:0.3g:76mL;
2) Preparing a graphite anode material with strong cohesiveness:
s1: mixing 8.5g of graphite, 0.7g of conductive agent and deionized water, feeding into a stirring tank, controlling the stirring speed to 260r/min, stirring at normal temperature for 0.5h, adding 0.8g of adhesive, controlling the stirring speed to 600r/min, and stirring at normal temperature for 1h to obtain graphite negative electrode slurry with the solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 350r/min, heating to 90 ℃, preserving heat for 3.5h, transferring into a vacuum drying oven, controlling the temperature to be 60 ℃, and drying for 6h to obtain a graphite anode material with strong cohesiveness;
comparative example 1
The preparation process of the graphite anode material with strong cohesiveness in the comparative example is as follows:
s1: mixing 8.5g of graphite, 0.7g of conductive agent and NVP, feeding the mixture into a stirring tank, controlling the stirring speed to 300r/min, stirring for 0.5h at normal temperature, adding 0.8g of polyvinylidene fluoride, controlling the stirring speed to 700r/min, and stirring for 1h at normal temperature to obtain graphite negative electrode slurry with the solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 300r/min, heating to 85 ℃, preserving heat for 4 hours, transferring into a vacuum drying oven, controlling the temperature to be 70 ℃, and drying for 8 hours to obtain a graphite anode material;
comparative example 2
The preparation process of the graphite anode material with strong cohesiveness in the comparative example is as follows:
s1: mixing 8g of graphite, 1g of a conductive agent and NVP, feeding the mixture into a stirring tank, controlling the stirring speed to be 200r/min, stirring for 0.5h at normal temperature, adding 1g of polyvinylidene fluoride, controlling the stirring speed to be 500r/min, and stirring for 1h at normal temperature to obtain graphite negative electrode slurry with the solid content of 50%;
s2: transferring the slurry into a reaction kettle, controlling the stirring reaction rate to be 300r/min, heating to 85 ℃, preserving heat for 3 hours, transferring into a vacuum drying oven, controlling the temperature to be 60 ℃, and drying for 6 hours to obtain a graphite anode material;
comparative example 3
The preparation process of the graphite anode material with strong cohesiveness in the comparative example is as follows:
s1: mixing 8g of graphite, 1g of a conductive agent and deionized water, feeding into a stirring tank, controlling the stirring speed to be 200r/min, stirring for 0.5h at normal temperature, adding 1g of a binder (the water-based binder in the patent application number 2023110113084.8 is selected as the comparative example), controlling the stirring speed to be 500r/min, and stirring for 1h at normal temperature to obtain graphite cathode slurry with the solid content of 50%;
s2: transferring the slurry into a drying oven, controlling the temperature to be 70 ℃, preserving heat for 3 hours, transferring into a vacuum drying oven, controlling the temperature to be 60 ℃, and drying for 6 hours to obtain a graphite anode material;
in order to facilitate testing of the relevant properties of the graphite anode materials with strong adhesion, the graphite anode materials prepared in examples 1 to 7 and comparative examples 1 to 3 were subjected to relevant property tests, and specific test data are shown in table 1:
capacity retention test:
the graphite negative electrode materials having strong adhesion prepared in examples 1 to 7 and the graphite negative electrode materials prepared in comparative examples 1 to 3 were scraped with 300. Mu.mThe knife was uniformly knife coated on copper foil, then dried and compacted in a vacuum oven at 100deg.C to give a negative electrode sheet, and then the negative electrode sheet and electrolyte (LiPF 6 ) And the lithium sheet is assembled into a lithium ion battery in a glove box, then the lithium ion battery is subjected to charge and discharge test at normal temperature, the charge and discharge voltage is 3.0-4.2V, and the lithium ion battery is subjected to test by circulating for 500 weeks with the current density of 1C.
Peel strength test:
and (3) taking the prepared negative plate, using an adhesive tape with the width of 20mm to adhere the prepared negative plate, tightly pressing and adhering the prepared negative plate, testing the negative plate by using a CMT6104 electronic stretcher, testing 5 times for each group at the stretching speed of 50 mm/min, and taking an average value.
Peel strength test after soaking the electrolyte:
and (3) taking the prepared negative plate, soaking the negative plate in electrolyte at 65 ℃ for 100 hours, using an adhesive tape with the width of 20mm to adhere the negative plate to the prepared negative plate, tightly pressing and firmly adhering the negative plate, using a CMT6104 electronic stretcher to test the negative plate, testing the negative plate at the stretching speed of 50 mm/min for 5 times, and taking an average value.
TABLE 1
As can be seen from Table 1, the graphite negative electrode materials with strong adhesion prepared in examples 1 to 7 had capacity retention rates of 81 to 92% after 500 weeks of circulation, which were superior to those prepared in comparative examples 1 to 2, and were not much different from those prepared in comparative example 3; the graphite negative electrode materials prepared in examples 1 to 7 were strong in adhesion and had ion conductivities of 62 to 71 S.cm -2 The difference between the graphite anode materials with strong cohesiveness prepared in comparative examples 1-3 is not large; however, the graphite negative electrode materials prepared in examples 1 to 7, which have strong adhesion, have peel strengths of 182 to 245N/m and peel strengths of 157 to 223N/m after immersing in an electrolyte, are superior to those prepared in comparative examples 1 to 3.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The graphite negative electrode material with strong cohesiveness is characterized by comprising, by weight, 75-85% of graphite, 8-13% of a binder and 7-12% of a conductive agent;
the preparation of the adhesive comprises the following steps:
step A1: mixing 2-hydroxy cinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone, heating to 60-75 ℃, stirring for reaction for 3-5h, and then drying in a drying oven at 65-70 ℃ to obtain a compound A;
step A2: mixing and feeding the compound A, the butenamide, the AIBN and the DMF, heating to 60-70 ℃, and stirring for reacting for 4-5 hours to obtain the binder.
2. The graphite negative electrode material with strong adhesion according to claim 1, wherein in step A1, the dosage ratio of 2-hydroxycinnamic acid, 2-perfluorooctyl ethanol, stannous oxide and acetone is 6-8.5g:17-23.5g:0.5-1g:70-85mL.
3. The graphite negative electrode material having strong adhesion according to claim 1, wherein in step A2, the amount ratio of compound a, butenamide, AIBN and DMF is 20-25g:3.5-5g:0.2-0.5g:65-80mL.
4. A method for preparing a graphite anode material with strong adhesion, which is characterized in that the graphite anode material according to any one of claims 1-3 comprises the following steps:
step S1: mixing graphite, a conductive agent and deionized water, feeding the mixture into a stirring tank, stirring the mixture for 0.5h at normal temperature, adding an adhesive, and stirring the mixture for 0.5-1h at normal temperature to obtain graphite cathode slurry;
step S2: transferring the slurry into a reaction kettle, stirring and reacting for 3-4h, transferring into a vacuum drying oven, and drying for 6-8h to obtain the graphite anode material.
5. The method for producing a strongly adhering graphite negative electrode material of claim 4, wherein in step S1, the solid content of the graphite negative electrode slurry is 50%.
6. The method for preparing a graphite negative electrode material with strong adhesion according to claim 4, wherein in step S2, the temperature of the reaction kettle is 85-95 ℃.
7. The method for producing a strongly adhering graphite negative electrode material of claim 4, wherein in step S2, the temperature of the vacuum drying oven is 60-70 ℃.
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