CN117586011A - Preparation process of high-performance graphite anode material - Google Patents
Preparation process of high-performance graphite anode material Download PDFInfo
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- CN117586011A CN117586011A CN202410065455.5A CN202410065455A CN117586011A CN 117586011 A CN117586011 A CN 117586011A CN 202410065455 A CN202410065455 A CN 202410065455A CN 117586011 A CN117586011 A CN 117586011A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 46
- 239000010439 graphite Substances 0.000 title claims abstract description 46
- 239000010405 anode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 11
- 238000007792 addition Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 56
- 229910021641 deionized water Inorganic materials 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 55
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000003607 modifier Substances 0.000 claims description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- -1 aminopropyl Chemical group 0.000 claims description 17
- 229920005575 poly(amic acid) Polymers 0.000 claims description 17
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 16
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 12
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 10
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000000203 mixture Substances 0.000 claims 2
- 238000004108 freeze drying Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002153 silicon-carbon composite material Substances 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 229910021389 graphene Inorganic materials 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 4
- 239000011229 interlayer Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 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 discloses a preparation process of a high-performance graphite anode material, which is characterized in that after natural graphite is treated, nitrogen doping treatment is carried out, more lithium storage sites can be introduced by nitrogen doping, the interlayer distance of graphene is enlarged, lithium ions are easy to detach in the charge and discharge process, tin oxide is loaded, the specific capacity of the anode material can be increased, a carbon-silicon composite layer coating is formed on the surface through thermal imidization and high-temperature carbonization of polyamide acid salt, the carbon-silicon composite layer coating can inhibit volume expansion of pretreated graphite during lithium removal, further tin oxide pulverization and falling off are prevented, the carbon-silicon composite layer on the surface is of a porous structure, a diffusion channel of lithium ions can be increased, stability of modified filler in electrolyte is protected, the multiplying power performance of the anode material is improved, the structure of the carbon-silicon composite layer on the surface is regulated through the addition of an intermediate 1 and epoxy cage type polysilsesquioxane, and the specific capacity of an electrode can be further improved.
Description
Technical Field
The invention relates to the technical field of preparation of negative electrode materials, in particular to a preparation process of a high-performance graphite negative electrode material.
Background
The lithium ion battery is used as a high-efficiency electric energy accommodating and converting container, namely an electric energy storage place is also electric energy release equipment, and the purpose of mutual conversion between electric energy and chemical energy can be achieved through reversible electrochemical intercalation reaction. Meanwhile, high electric energy load is a key characteristic of lithium ion batteries, which are widely used for electric energy supply of various forms of power consuming devices. The future application of lithium ion battery is wide, and there are two application fields, namely electric energy storage and energy supply for mobile energy storage system and fixed large-scale energy storage system. The lithium ion battery is used as a high-efficiency electric energy accommodating and converting container, namely an electric energy storage place is also electric energy releasing equipment, the purpose of mutual conversion between electric energy and chemical energy can be achieved through reversible electrochemical intercalation reaction, the multiplying power performance of the existing graphite is poor, the existing graphite is difficult to meet the demand of a fast charging market, and the technical defect of poor multiplying power performance of the graphite can severely restrict the popularization of the electric automobile especially under the age background of high-speed development of the electric automobile.
Disclosure of Invention
The invention aims to provide a preparation process of a high-performance graphite anode material, which solves the problem that the anode material can continuously collapse according to expansion after long-time use at the present stage, so that the service life of a battery is low.
The aim of the invention can be achieved by the following technical scheme:
a preparation process of a high-performance graphite anode material specifically comprises the following steps:
step A1: mixing diphenyl dichlorosilane, KH572 and deionized water, stirring for 10-15min at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding concentrated sulfuric acid and 1, 3-bis (aminopropyl) tetramethyl disilyl ether, reacting for 4-6h, regulating pH to be neutral to obtain an intermediate 1, uniformly mixing deionized water, tetraethyl ammonium hydroxide and isopropanol, stirring and adding KH560 at the rotation speed of 200-300r/min and the temperature of 30-35 ℃, stirring for 4-6h, heating to 75-80 ℃, reacting for 15-20h, and filtering to remove filtrate to obtain the epoxy cage polysilsesquioxane;
step A2: uniformly mixing an intermediate 1, epoxy cage polysilsesquioxane and DMF (dimethyl formamide), reacting for 5-7h at the rotating speed of 150-200r/min and the temperature of 30-40 ℃ and the pH value of 11-12, distilling under reduced pressure to obtain a modifier, mixing the modifier, 3, 4-diphenyl tetracarboxylic dianhydride and N, N-dimethylacetamide, stirring for 2-4h at the rotating speed of 300-500r/min and the temperature of 0-3 ℃, heating to 20-25 ℃, adding triethylamine, continuously reacting for 3-4h, adding the reaction product into acetone, standing for 2-3h, and filtering to remove filtrate to obtain polyamic acid salt;
step A3: mixing polyamic acid salt, modified filler, triethylamine and deionized water, stirring for 1-1.5h under the irradiation of 365nm ultraviolet light at 500-800r/min, pouring into a mould, preserving heat for 20-25h at minus 196 ℃, drying for 10-15h at minus 15 ℃ under the vacuum degree of 2-3Pa, placing into a tube furnace, preserving heat for 2-3h at 220-250 ℃, heating to 950-1000 ℃ and carbonizing for 3-5h to obtain the high-performance graphite anode material.
Further, the dosage ratio of diphenyldichlorosilane, KH572 deionized water and 1, 3-bis (aminopropyl) tetramethyl disilyl ether in the step A1 is 2mmol, 1mmol, 20mL, 2mmol, the dosage of concentrated sulfuric acid is 1-1.5% of the mass sum of diphenyldichlorosilane, KH572 and 1, 3-bis (aminopropyl) tetramethyl disilyl ether, and the mass ratio of deionized water, tetraethylammonium hydroxide, isopropanol and KH560 is 10:0.21:32:40.25.
Further, the molar ratio of the intermediate 1 to the epoxy cage polysilsesquioxane in the step A2 is 8:1, and the molar ratio of the modifier, 3, 4-biphenyltetracarboxylic dianhydride and triethylamine is 1:8:8.3.
Further, the dosage ratio of the polyamic acid salt, the modified filler and the deionized water in the step A3 is 10 g/2 g/0.3 g/200 mL.
Further, the modified filler is prepared by the following steps:
step B1: uniformly mixing natural graphite, sodium nitrate and concentrated sulfuric acid, stirring and adding potassium permanganate at the rotation speed of 150-200r/min and the temperature of 0-3 ℃, stirring for 2-3 hours, heating to 35-40 ℃, adding deionized water, heating to 95-98 ℃ after the addition is finished, stirring for 30-40 minutes, adding hydrogen peroxide, continuously stirring for 1-1.5 hours, and filtering to remove filtrate to obtain pretreated graphite;
step B2: uniformly mixing pretreated graphite, polyvinylpyrrolidone and methanol, adding zinc nitrate hexahydrate and 2-methylimidazole, stirring for 4-6 hours at the rotating speed of 200-300r/min and the temperature of 20-25 ℃, filtering to remove filtrate, preserving the temperature of a substrate for 4-6 hours at the temperature of 800-850 ℃ under the protection of argon, soaking in hydrochloric acid solution for 10-15 hours, filtering and washing to neutrality, and thus obtaining modified graphite;
step B3: dispersing stannous oxalate in deionized water, adding citric acid solution, mixing uniformly, regulating pH to be neutral, adding modified graphite, carrying out ultrasonic treatment for 3-5h under the condition of the frequency of 20-30kHz, filtering to remove filtrate, preserving heat for 2-3h under the condition of the temperature of 400-450 ℃ to obtain a modified matrix, dispersing the modified matrix in ethanol, stirring and adding 3-mercaptopropyl triethoxysilane and deionized water under the condition of the rotating speed of 200-300r/min and the temperature of 50-60 ℃ to react for 1-1.5h to obtain the modified filler.
Further, the dosage ratio of the natural graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide in the step B1 is 1g to 0.5g to 26mL to 3g to 46mL to 10mL, and the mass fraction of the hydrogen peroxide is 30%.
Further, the dosage ratio of the pretreated graphite, polyvinylpyrrolidone, methanol, zinc nitrate hexahydrate and 2-methylimidazole in the step B2 is 40mg:50mg:40mL:0.73g:0.85g, and the concentration of the hydrochloric acid solution is 2mol/L.
Further, the dosage ratio of stannous oxalate, deionized water, citric acid solution and modified graphite in the step B3 is 1.2g:2.5mL:5mL:1g, and the dosage of 3-mercaptopropyl triethoxysilane is 3% of the mass of the modified graphite.
The invention has the beneficial effects that: the high-performance graphite anode material prepared by the invention takes diphenyl dichlorosilane and KH572 as raw materials, is hydrolyzed firstly, is then polymerized with 1, 3-bis (aminopropyl) tetramethyl disilyl ether under the action of concentrated sulfuric acid to form amino-terminated polysiloxane, an intermediate 1 is prepared, KH560 is hydrolyzed and polymerized to form cage-shaped polysilsesquioxane, the intermediate 1 and epoxy cage-shaped polysilsesquioxane are reacted under alkaline condition, so that amino on the intermediate 1 is reacted with epoxy on the epoxy cage-shaped polysilsesquioxane to form a hyperbranched structure taking the cage-shaped siloxane as a center, a modifier is prepared, the modifier is reacted with 3, 4-diphenyl tetracarboxylic dianhydride, the ring opening of 3, 4-diphenyl tetracarboxylic dianhydride is reacted with amino on the modifier, a polyamic acid salt structure is formed by taking the cage-shaped siloxane as a center, the polyamic acid salt and modified filler are blended and stirred, and irradiating with 365nm ultraviolet light to graft double bond on polyamide acid salt with mercapto on modified filler to form organic coating inorganic structure, heating to thermally imidize organic molecular chain, carbonizing at high temperature to form carbon coating to obtain modified filler, treating the modified filler with natural graphene as raw material to obtain pretreated graphite, treating the pretreated graphite with 2-methylimidazole to form nitrogen doped state to obtain modified graphite, attaching tin oxide to the surface of the modified graphite by stannous oxalate hydrothermal method, treating the surface of the modified graphite with KH572 to form surface machined mercapto to obtain modified filler, treating the modified filler with nitrogen doping to introduce more lithium storage sites and enlarge graphene layer spacing to facilitate lithium ion deintercalation in charging and discharging process, and tin oxide is loaded, the specific capacity of the anode material can be increased, a carbon-silicon composite layer coating is formed on the surface through thermal imidization and high-temperature carbonization of polyamide acid salt, the carbon-silicon composite layer coating can inhibit volume expansion of pretreated graphite during lithium intercalation, further tin oxide pulverization and exfoliation are prevented, the carbon-silicon composite layer on the surface is of a porous structure, a diffusion channel of lithium ions can be increased, the stability of modified filler in electrolyte is protected, the rate capability of the anode material is improved, the structure of the carbon-silicon composite layer on the surface is regulated through the addition of an intermediate 1 and epoxy cage type polysilsesquioxane, and the specific capacity of an electrode can be further improved.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but 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
A preparation process of a high-performance graphite anode material specifically comprises the following steps:
step A1: mixing diphenyl dichlorosilane, KH572 and deionized water, stirring for 10min at the temperature of 60 ℃ at the rotation speed of 200r/min, adding concentrated sulfuric acid and 1, 3-bis (aminopropyl) tetramethyl disilyl ether, reacting for 4h, adjusting pH to be neutral to obtain an intermediate 1, uniformly mixing deionized water, tetraethyl ammonium hydroxide and isopropanol, stirring and adding KH560 at the temperature of 30 ℃ at the rotation speed of 200r/min, stirring for 4h, heating to 75 ℃, reacting for 15h, and filtering to remove filtrate to obtain the epoxy cage type polysilsesquioxane;
step A2: uniformly mixing an intermediate 1, epoxy cage polysilsesquioxane and DMF (dimethyl formamide), reacting for 5 hours at the rotating speed of 150r/min and the temperature of 30 ℃ and the pH value of 11, distilling under reduced pressure to obtain a modifier, mixing the modifier, 3, 4-biphenyl tetracarboxylic dianhydride and N, N-dimethylacetamide, stirring for 2 hours at the rotating speed of 300r/min and the temperature of 0 ℃, heating to 20 ℃, adding triethylamine, continuously reacting for 3 hours, adding a reaction product into acetone, standing for 2 hours, and filtering to remove filtrate to obtain polyamic acid salt;
step A3: mixing polyamic acid salt, modified filler, triethylamine and deionized water, stirring for 1h under the irradiation of 365nm ultraviolet light at 500r/min, pouring into a mould, preserving heat for 20h under the temperature of minus 196 ℃, drying for 10h under the temperature of minus 15 ℃ and the vacuum degree of 2Pa, placing into a tube furnace, preserving heat for 2h under the temperature of 220 ℃, heating to 950 ℃, and carbonizing for 3h to obtain the high-performance graphite anode material.
The dosage ratio of the diphenyldichlorosilane, KH572 deionized water and the 1, 3-bis (aminopropyl) tetramethyl disilyl ether in the step A1 is 2mmol, 1mmol, 20mL, 2mmol, the dosage of the concentrated sulfuric acid is 1% of the sum of the diphenyldichlorosilane, KH572 and the 1, 3-bis (aminopropyl) tetramethyl disilyl ether, and the mass ratio of the deionized water, tetraethylammonium hydroxide, isopropanol and KH560 is 10:0.21:32:40.25.
The molar ratio of the intermediate 1 to the epoxy cage polysilsesquioxane in the step A2 is 8:1, and the molar ratio of the modifier, 3, 4-diphenyl tetracarboxylic dianhydride and triethylamine is 1:8:8.3.
The dosage ratio of the polyamic acid salt, the modified filler and the deionized water in the step A3 is 10g:2g:0.3g:200mL.
The modified filler is prepared by the following steps:
step B1: uniformly mixing natural graphite, sodium nitrate and concentrated sulfuric acid, stirring at a rotating speed of 150r/min and a temperature of 0 ℃, adding potassium permanganate, stirring for 2 hours, heating to 35 ℃, adding deionized water, heating to 95 ℃ after the addition is finished, stirring for 30 minutes, adding hydrogen peroxide, continuously stirring for 1 hour, and filtering to remove filtrate to obtain pretreated graphite;
step B2: uniformly mixing pretreated graphite, polyvinylpyrrolidone and methanol, adding zinc nitrate hexahydrate and 2-methylimidazole, stirring for 4 hours at the rotating speed of 200r/min and the temperature of 20 ℃, filtering to remove filtrate, preserving the temperature of a substrate for 4 hours under the argon protection condition at the temperature of 800 ℃, soaking in hydrochloric acid solution for 10 hours, filtering and washing to neutrality, and thus obtaining modified graphite;
step B3: dispersing stannous oxalate in deionized water, adding citric acid solution, mixing uniformly, regulating pH to be neutral, adding modified graphite, carrying out ultrasonic treatment for 3 hours under the condition of the frequency of 20kHz, filtering to remove filtrate, carrying out heat preservation on a substrate at the temperature of 400 ℃ for 2 hours to obtain a modified matrix, dispersing the modified matrix in ethanol, stirring and adding 3-mercaptopropyl triethoxysilane and deionized water under the condition of the rotating speed of 200r/min and the temperature of 50 ℃ for reaction for 1 hour to obtain the modified filler.
The dosage ratio of the natural graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide in the step B1 is 1g to 0.5g to 26mL to 3g to 46mL to 10mL, and the mass fraction of the hydrogen peroxide is 30%.
The dosage ratio of the pretreated graphite, polyvinylpyrrolidone, methanol, zinc nitrate hexahydrate and 2-methylimidazole in the step B2 is 40 mg/50 mg/40 mL/0.73 g/0.85 g, and the concentration of the hydrochloric acid solution is 2mol/L.
The dosage ratio of stannous oxalate, deionized water, citric acid solution and modified graphite in the step B3 is 1.2g:2.5mL:5mL:1g, and the dosage of 3-mercaptopropyl triethoxysilane is 3% of the mass of the modified graphite.
Example 2
A preparation process of a high-performance graphite anode material specifically comprises the following steps:
step A1: mixing diphenyl dichlorosilane, KH572 and deionized water, stirring at a rotation speed of 200r/min and a temperature of 65 ℃ for 13min, adding concentrated sulfuric acid and 1, 3-bis (aminopropyl) tetramethyl disilyl ether, reacting for 5h, adjusting pH to be neutral to obtain an intermediate 1, uniformly mixing deionized water, tetraethyl ammonium hydroxide and isopropanol, stirring at a rotation speed of 200r/min and a temperature of 34 ℃ and adding KH560, stirring for 5h, heating to 78 ℃ for reacting for 18h, and filtering to remove filtrate to obtain epoxy cage type polysilsesquioxane;
step A2: uniformly mixing an intermediate 1, epoxy cage polysilsesquioxane and DMF (dimethyl formamide), reacting for 6 hours at the rotating speed of 150r/min and the temperature of 35 ℃ and the pH value of 12, distilling under reduced pressure to obtain a modifier, mixing the modifier, 3, 4-biphenyl tetracarboxylic dianhydride and N, N-dimethylacetamide, stirring for 3 hours at the rotating speed of 300r/min and the temperature of 2 ℃, heating to 25 ℃, adding triethylamine, continuously reacting for 3 hours, adding a reaction product into acetone, standing for 3 hours, and filtering to remove filtrate to obtain polyamic acid salt;
step A3: mixing polyamic acid salt, modified filler, triethylamine and deionized water, stirring for 1.5 hours under the irradiation of 365nm ultraviolet light at the rotating speed of 500r/min, pouring into a mould, preserving heat for 20 hours under the temperature of minus 196 ℃, drying for 10 hours under the temperature of minus 15 ℃ and the vacuum degree of 3Pa, placing into a tubular furnace, preserving heat for 2 hours under the temperature of 250 ℃, heating to 980 ℃, and carbonizing for 4 hours to obtain the high-performance graphite anode material.
The dosage ratio of the diphenyldichlorosilane, KH572 deionized water and the 1, 3-bis (aminopropyl) tetramethyl disilyl ether in the step A1 is 2mmol, 1mmol, 20mL, 2mmol, the dosage of the concentrated sulfuric acid is 1.3 percent of the mass sum of the diphenyldichlorosilane, KH572 and the 1, 3-bis (aminopropyl) tetramethyl disilyl ether, and the mass ratio of the deionized water, tetraethylammonium hydroxide, isopropanol and KH560 is 10:0.21:32:40.25.
The molar ratio of the intermediate 1 to the epoxy cage polysilsesquioxane in the step A2 is 8:1, and the molar ratio of the modifier, 3, 4-diphenyl tetracarboxylic dianhydride and triethylamine is 1:8:8.3.
The dosage ratio of the polyamic acid salt, the modified filler and the deionized water in the step A3 is 10g:2g:0.3g:200mL.
The modified filler is prepared by the following steps:
step B1: uniformly mixing natural graphite, sodium nitrate and concentrated sulfuric acid, stirring at a rotating speed of 200r/min and a temperature of 2 ℃, adding potassium permanganate, stirring for 2 hours, heating to 40 ℃, adding deionized water, heating to 95 ℃ after the addition is finished, stirring for 35 minutes, adding hydrogen peroxide, continuously stirring for 1.3 hours, and filtering to remove filtrate to obtain pretreated graphite;
step B2: uniformly mixing pretreated graphite, polyvinylpyrrolidone and methanol, adding zinc nitrate hexahydrate and 2-methylimidazole, stirring at a rotation speed of 200r/min and a temperature of 25 ℃ for 5 hours, filtering to remove filtrate, preserving the temperature of a substrate at 830 ℃ under the protection of argon for 5 hours, soaking in hydrochloric acid solution for 13 hours, filtering and washing to neutrality, and thus obtaining modified graphite;
step B3: dispersing stannous oxalate in deionized water, adding citric acid solution, mixing uniformly, regulating pH to be neutral, adding modified graphite, carrying out ultrasonic treatment for 4 hours under the condition of the frequency of 25kHz, filtering to remove filtrate, keeping the temperature of a substrate at 430 ℃ for 2.5 hours to obtain a modified matrix, dispersing the modified matrix in ethanol, stirring and adding 3-mercaptopropyl triethoxysilane and deionized water under the condition of the rotating speed of 200r/min and the temperature of 55 ℃ to react for 1.3 hours to obtain the modified filler.
The dosage ratio of the natural graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide in the step B1 is 1g to 0.5g to 26mL to 3g to 46mL to 10mL, and the mass fraction of the hydrogen peroxide is 30%.
The dosage ratio of the pretreated graphite, polyvinylpyrrolidone, methanol, zinc nitrate hexahydrate and 2-methylimidazole in the step B2 is 40 mg/50 mg/40 mL/0.73 g/0.85 g, and the concentration of the hydrochloric acid solution is 2mol/L.
The dosage ratio of stannous oxalate, deionized water, citric acid solution and modified graphite in the step B3 is 1.2g:2.5mL:5mL:1g, and the dosage of 3-mercaptopropyl triethoxysilane is 3% of the mass of the modified graphite.
Example 3
A preparation process of a high-performance graphite anode material specifically comprises the following steps:
step A1: mixing diphenyl dichlorosilane, KH572 and deionized water, stirring for 15min at the temperature of 70 ℃ at the rotation speed of 300r/min, adding concentrated sulfuric acid and 1, 3-bis (aminopropyl) tetramethyl disilyl ether, reacting for 6h, adjusting pH to be neutral to obtain an intermediate 1, uniformly mixing deionized water, tetraethyl ammonium hydroxide and isopropanol, stirring and adding KH560 at the temperature of 35 ℃ at the rotation speed of 300r/min, stirring for 6h, heating to 80 ℃, reacting for 20h, and filtering to remove filtrate to obtain the epoxy cage type polysilsesquioxane;
step A2: uniformly mixing an intermediate 1, epoxy cage polysilsesquioxane and DMF (dimethyl formamide), reacting for 7h at the rotation speed of 200r/min and the temperature of 40 ℃ and the pH value of 12, distilling under reduced pressure to obtain a modifier, mixing the modifier, 3, 4-biphenyl tetracarboxylic dianhydride and N, N-dimethylacetamide, stirring for 4h at the rotation speed of 500r/min and the temperature of 3 ℃, heating to 25 ℃, adding triethylamine, continuously reacting for 4h, adding a reaction product into acetone, standing for 3h, and filtering to remove filtrate to obtain polyamic acid salt;
step A3: mixing polyamic acid salt, modified filler, triethylamine and deionized water, stirring for 1.5 hours under the irradiation of 365nm ultraviolet light at the rotating speed of 800r/min, pouring into a mould, preserving heat for 25 hours under the temperature of minus 196 ℃, drying for 15 hours under the temperature of minus 15 ℃ and the vacuum degree of 3Pa, placing into a tubular furnace, preserving heat for 3 hours under the temperature of 250 ℃, heating to 1000 ℃ and carbonizing for 5 hours to obtain the high-performance graphite anode material.
The dosage ratio of the diphenyldichlorosilane, KH572 deionized water and the 1, 3-bis (aminopropyl) tetramethyl disilyl ether in the step A1 is 2mmol, 1mmol, 20mL, 2mmol, the dosage of the concentrated sulfuric acid is 1.5 percent of the sum of the diphenyldichlorosilane, KH572 and the 1, 3-bis (aminopropyl) tetramethyl disilyl ether, and the mass ratio of the deionized water, tetraethylammonium hydroxide, isopropanol and KH560 is 10:0.21:32:40.25.
The molar ratio of the intermediate 1 to the epoxy cage polysilsesquioxane in the step A2 is 8:1, and the molar ratio of the modifier, 3, 4-diphenyl tetracarboxylic dianhydride and triethylamine is 1:8:8.3.
The dosage ratio of the polyamic acid salt, the modified filler and the deionized water in the step A3 is 10g:2g:0.3g:200mL.
The modified filler is prepared by the following steps:
step B1: uniformly mixing natural graphite, sodium nitrate and concentrated sulfuric acid, stirring at a rotating speed of 200r/min and a temperature of 3 ℃, adding potassium permanganate, stirring for 3 hours, heating to 40 ℃, adding deionized water, heating to 98 ℃ after the addition is finished, stirring for 40 minutes, adding hydrogen peroxide, continuously stirring for 1.5 hours, and filtering to remove filtrate to obtain pretreated graphite;
step B2: uniformly mixing pretreated graphite, polyvinylpyrrolidone and methanol, adding zinc nitrate hexahydrate and 2-methylimidazole, stirring at a rotation speed of 300r/min and a temperature of 25 ℃ for 6 hours, filtering to remove filtrate, preserving the temperature of a substrate at 850 ℃ under the protection of argon for 6 hours, soaking in hydrochloric acid solution for 15 hours, filtering and washing to neutrality, and thus obtaining modified graphite;
step B3: dispersing stannous oxalate in deionized water, adding citric acid solution, mixing uniformly, regulating pH to be neutral, adding modified graphite, carrying out ultrasonic treatment for 5 hours under the condition of the frequency of 30kHz, filtering to remove filtrate, carrying out heat preservation on a substrate at the temperature of 450 ℃ for 3 hours to obtain a modified matrix, dispersing the modified matrix in ethanol, stirring and adding 3-mercaptopropyl triethoxysilane and deionized water under the condition of the rotating speed of 300r/min and the temperature of 60 ℃ to react for 1.5 hours to obtain the modified filler.
The dosage ratio of the natural graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide in the step B1 is 1g to 0.5g to 26mL to 3g to 46mL to 10mL, and the mass fraction of the hydrogen peroxide is 30%.
The dosage ratio of the pretreated graphite, polyvinylpyrrolidone, methanol, zinc nitrate hexahydrate and 2-methylimidazole in the step B2 is 40 mg/50 mg/40 mL/0.73 g/0.85 g, and the concentration of the hydrochloric acid solution is 2mol/L.
The dosage ratio of stannous oxalate, deionized water, citric acid solution and modified graphite in the step B3 is 1.2g:2.5mL:5mL:1g, and the dosage of 3-mercaptopropyl triethoxysilane is 3% of the mass of the modified graphite.
Comparative example 1
This comparative example uses intermediate 1 instead of modifier as compared to example 1, the rest of the procedure being the same.
Comparative example 2
This comparative example uses phenylenediamine instead of modifier as compared to example 1, with the remainder of the procedure being the same.
Comparative example 3
This comparative example uses pretreated graphite instead of modified graphite as compared to example 1, and the rest of the procedure is the same.
The negative electrode materials prepared in examples 1-3 and comparative examples 1-3, carboxymethyl cellulose, conductive carbon black and styrene-butadiene rubber were magnetically stirred in deionized water for 8 hours according to a mass ratio of 95:1.5:1.5:2, and were uniformly mixed. The slurry obtained by mixing was coated on a copper foil, and vacuum-dried at 60 ℃ to obtain a working electrode. Adopting metallic lithium as a counter electrode, adopting Celgard2325 as a diaphragm, adopting 1mol/L LiPF6-EC (ethylene carbonate)/DMC (dimethyl carbonate)/EMC (ethylmethyl carbonate) (the volume ratio is 1:1:1), completing CR2016 type button half-cell assembly in a glove box filled with high-purity argon, and assembling the assembled button cell;
discharging the battery sample to 0.01V at a constant current of 0.05C, and recording the obtained capacity as a charging capacity of 0.05C; then standing for 5min, and charging to 3.0V at a constant current of 0.1C, wherein the obtained capacity is recorded as 0.1C discharge capacity; and finally stopping operation, wherein the first coulombic efficiency is 0.05C charge capacity/0.1C discharge capacity.
Discharging to 0.01V at 0.1C constant current, standing for 5min, and then charging to 3.0V at 0.1C constant current; standing for 5min, and discharging to 0.01V at constant current of 0.1C to obtain discharge capacity corresponding to 0.1C; and finally stopping the operation, and recording the discharge capacity corresponding to the discharge capacity of 0.1C for the second time.
Discharging to 0.01V at 0.2C constant current, standing for 5min, and then charging to 3.0V at 0.2C constant current; standing for 5min, and discharging to 0.01V at constant current of 0.2C to obtain discharge capacity corresponding to 0.2C; and finally stopping the operation, and recording the discharge capacity corresponding to the discharge capacity of 0.2C for the second time.
Discharging to 0.01V at 0.2C constant current, standing for 5min, and then charging to 3.0V at 0.2C constant current; the above steps are sequentially repeated for 500 times and 800 times, the discharge capacity is recorded, the capacity retention rate is calculated, and the detection results are shown in the following table;
the table shows that the lithium ion battery has good lithium ion capacity and long service life.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (8)
1. A preparation process of a high-performance graphite anode material is characterized by comprising the following steps of: the method specifically comprises the following steps:
step A1: mixing and stirring diphenyl dichlorosilane, KH572 and deionized water, adding concentrated sulfuric acid and 1, 3-bis (aminopropyl) tetramethyl disilyl ether, reacting, adjusting pH to be neutral to obtain an intermediate 1, mixing and stirring deionized water, tetraethyl ammonium hydroxide and isopropanol, adding KH560, stirring, heating for reacting, and filtering to remove filtrate to obtain epoxy cage polysilsesquioxane;
step A2: mixing intermediate 1, epoxy cage polysilsesquioxane and DMF for reaction, distilling under reduced pressure to obtain a modifier, mixing and stirring the modifier, 3, 4-diphenyl tetracarboxylic dianhydride and N, N-dimethylacetamide, heating and adding triethylamine, continuing the reaction, adding the reaction product into acetone, standing for treatment, and filtering to remove filtrate to obtain polyamic acid salt;
step A3: and (3) mixing and stirring the polyamic acid salt, the modified filler, the triethylamine and the deionized water, pouring the mixture into a die, freeze-drying, heating and preserving heat, and carbonizing the mixture to obtain the high-performance graphite anode material.
2. The process for preparing a high-performance graphite anode material according to claim 1, wherein the process comprises the following steps: the dosage ratio of the diphenyldichlorosilane to KH572 deionized water to the 1, 3-bis (aminopropyl) tetramethyl disilyl ether in the step A1 is 2mmol, 1mmol, 20mL, 2mmol, the dosage of the concentrated sulfuric acid is 1-1.5% of the mass sum of the diphenyldichlorosilane to KH572 and the 1, 3-bis (aminopropyl) tetramethyl disilyl ether, and the mass ratio of the deionized water to tetraethylammonium hydroxide to the isopropanol to KH560 is 10:0.21:32:40.25.
3. The process for preparing a high-performance graphite anode material according to claim 1, wherein the process comprises the following steps: the molar ratio of the intermediate 1 to the epoxy cage polysilsesquioxane in the step A2 is 8:1, and the molar ratio of the modifier, 3, 4-diphenyl tetracarboxylic dianhydride and triethylamine is 1:8:8.3.
4. The process for preparing a high-performance graphite anode material according to claim 1, wherein the process comprises the following steps: the dosage ratio of the polyamic acid salt, the modified filler and the deionized water in the step A3 is 10g:2g:0.3g:200mL.
5. The process for preparing a high-performance graphite anode material according to claim 1, wherein the process comprises the following steps: the modified filler is prepared by the following steps:
step B1: mixing and stirring natural graphite, sodium nitrate and concentrated sulfuric acid, adding potassium permanganate, stirring, heating, adding deionized water, heating continuously after the addition, stirring, adding hydrogen peroxide, stirring continuously, filtering to remove filtrate, and obtaining pretreated graphite;
step B2: uniformly mixing pretreated graphite, polyvinylpyrrolidone and methanol, adding zinc nitrate hexahydrate and 2-methylimidazole, stirring, filtering to remove filtrate, performing heat preservation on a substrate, soaking in hydrochloric acid solution, filtering, and washing to neutrality to obtain modified graphite;
step B3: dispersing stannous oxalate in deionized water, adding citric acid solution, mixing uniformly, adjusting pH to be neutral, adding modified graphite, carrying out ultrasonic treatment, filtering to remove filtrate, carrying out heat preservation treatment on a substrate to obtain a modified matrix, dispersing the modified matrix in ethanol, stirring, adding 3-mercaptopropyl triethoxysilane and deionized water, and carrying out reaction to obtain the modified filler.
6. The process for preparing the high-performance graphite anode material according to claim 5, wherein the process comprises the following steps: the dosage ratio of the natural graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate, deionized water and hydrogen peroxide in the step B1 is 1g to 0.5g to 26mL to 3g to 46mL to 10mL.
7. The process for preparing the high-performance graphite anode material according to claim 5, wherein the process comprises the following steps: the dosage ratio of pretreated graphite, polyvinylpyrrolidone, methanol, zinc nitrate hexahydrate and 2-methylimidazole described in step B2 was 40mg:50mg:40mL:0.73g:0.85g.
8. The process for preparing the high-performance graphite anode material according to claim 5, wherein the process comprises the following steps: the dosage ratio of stannous oxalate, deionized water, citric acid solution and modified graphite in the step B3 is 1.2g:2.5mL:5mL:1g, and the dosage of 3-mercaptopropyl triethoxysilane is 3% of the mass of the modified graphite.
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