CN114122357A - Lithium salt-coated graphene-doped silicon-carbon composite material and preparation method thereof - Google Patents
Lithium salt-coated graphene-doped silicon-carbon composite material and preparation method thereof Download PDFInfo
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- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 53
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 53
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 17
- 238000002347 injection Methods 0.000 claims abstract description 15
- 239000007924 injection Substances 0.000 claims abstract description 15
- 238000007740 vapor deposition Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229940091250 magnesium supplement Drugs 0.000 claims description 8
- 229910021426 porous silicon Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- VUNOFAIHSALQQH-UHFFFAOYSA-N Ethyl menthane carboxamide Chemical compound CCNC(=O)C1CC(C)CCC1C(C)C VUNOFAIHSALQQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 claims description 4
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 4
- 229960000869 magnesium oxide Drugs 0.000 claims description 4
- 235000012245 magnesium oxide Nutrition 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- CQQUWTMMFMJEFE-UHFFFAOYSA-N 2-chloro-n,n-diethylacetamide Chemical compound CCN(CC)C(=O)CCl CQQUWTMMFMJEFE-UHFFFAOYSA-N 0.000 claims description 3
- HKQZJXVIXAPOPZ-UHFFFAOYSA-N 3-amino-2,2-dimethylpropanamide Chemical compound NCC(C)(C)C(N)=O HKQZJXVIXAPOPZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 2
- IIUJCQYKTGNRHH-UHFFFAOYSA-N 2,4-dihydroxybenzamide Chemical compound NC(=O)C1=CC=C(O)C=C1O IIUJCQYKTGNRHH-UHFFFAOYSA-N 0.000 claims description 2
- DRYMMXUBDRJPDS-UHFFFAOYSA-N 2-hydroxy-2-methylpropanamide Chemical compound CC(C)(O)C(N)=O DRYMMXUBDRJPDS-UHFFFAOYSA-N 0.000 claims description 2
- GUCPYIYFQVTFSI-UHFFFAOYSA-N 4-methoxybenzamide Chemical compound COC1=CC=C(C(N)=O)C=C1 GUCPYIYFQVTFSI-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- WMSPXQIQBQAWLL-UHFFFAOYSA-N cyclopropanesulfonamide Chemical compound NS(=O)(=O)C1CC1 WMSPXQIQBQAWLL-UHFFFAOYSA-N 0.000 claims description 2
- 229950001902 dimevamide Drugs 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 238000002513 implantation Methods 0.000 claims description 2
- GWLOGZRVYXAHRE-UHFFFAOYSA-N n,4-dimethylbenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=C(C)C=C1 GWLOGZRVYXAHRE-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- IPWFJLQDVFKJDU-UHFFFAOYSA-N pentanamide Chemical compound CCCCC(N)=O IPWFJLQDVFKJDU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
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- 239000000463 material Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
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- 238000007599 discharging Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
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- 239000010406 cathode material Substances 0.000 description 2
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- -1 stirring and pulping Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C01B33/00—Silicon; Compounds thereof
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- C01B33/023—Preparation by reduction of silica or free silica-containing material
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
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Abstract
The invention discloses a lithium salt-coated graphene-doped silicon-carbon composite material and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, preparing carboxylic acid porous nano-silicon, then soaking the carboxylic acid porous nano-silicon in a solution of a catalyst amino organic solvent, then growing graphene with a vertical structure on the surface of the carboxylic acid porous nano-silicon by a vapor deposition method, finally depositing inorganic lithium salt on the surface of the carboxylic acid porous nano-silicon by a particle injection method, and crushing the inorganic lithium salt to obtain the lithium salt-coated graphene doped silicon-carbon composite material. The prepared composite material vertically grows graphene on the surface of the nanometer silicon by utilizing the action of the catalyst, so that the impedance and the expansion of the graphene are reduced; simultaneously, the carboxylic acid porous nano silicon and the amination solution are subjected to chemical reaction to generate an inner core with a stable structure; the impedance of the graphene is reduced by utilizing the synergistic effect of the electronic conductivity of the graphene and the high ionic conductivity of inorganic lithium salt on the shell of the graphene, and lithium ions can be rapidly inserted and removed through the inorganic lithium salt by depending on the core porous structure of the graphene, so that the quick charging performance is improved, and the expansion is reduced.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a lithium salt-coated graphene-doped silicon-carbon composite material and a preparation method thereof.
Background
The silicon-carbon cathode material has the advantages of high specific capacity, wide material source and the like, so the silicon-carbon cathode material is widely applied to the fields of high-end digital and high-energy density power batteries and the like, but the rate capability and the cycle performance deviation of the lithium ion battery are caused by the defects of poor conductivity, large expansion, low first efficiency and the like of silicon-carbon.
One of the measures for improving the multiplying power and the cycle performance of the silicon-carbon material is coating and doping modification of the material. The traditional coating method is to coat a layer of material with high conductivity on the surface of the core silicon through liquid phase and gas phase, and the defects of poor coating integrity, poor uniformity and the like exist, so that the coating layer and the core layer are easy to fall off due to expansion in the charging and discharging processes, and the cycle performance and the like of the coating layer and the core layer are influenced. The particle implantation method, that is, a layer of amorphous carbon or oxide is deposited on the surface of silicon or graphite, which has the characteristics of thin deposition thickness, good consistency, high conductivity, no chemical reaction between the deposited material and a base material, and the like, and the process is controllable, different materials and different thicknesses can be deposited according to the requirements of the materials, so as to achieve the customized development of the materials.
Disclosure of Invention
Aiming at the defects of poor conductivity, large expansion rate and the like of the existing silicon-carbon material, the invention provides a lithium salt-coated graphene-doped silicon-carbon composite material, which is mainly characterized in that the electronic conductivity of the material is improved by growing graphene on the surface of a porous nano silicon, and lithium salt is embedded into the surface of the graphene-doped silicon-carbon by a particle injection method, so that the expansion rate of the material as a battery material is reduced, and the specific capacity and the primary efficiency are improved.
The lithium salt-coated graphene-doped silicon-carbon composite material is characterized in that the silicon-carbon negative electrode material is of a core-shell structure, the inner core is graphene-doped nano-silicon, the outer shell is lithium salt, and the mass ratio of the outer layer is (1-10) wt%.
The mass ratio of graphene to nano silicon in the core is (1-5) to (95-99);
a preparation method of a lithium salt-coated graphene-doped silicon-carbon composite material is characterized by comprising the following steps:
(1) preparation of carboxylated porous nano-silicon A:
grinding metal magnesium and silicon dioxide in a high-speed grinding machine for 1-48 h, transferring the ground metal magnesium and silicon dioxide into a tubular furnace, heating to 400-600 ℃ in an argon atmosphere for thermal reduction for 1-48 h, adding the obtained product into a nitric acid solution, soaking and pickling to remove the metal magnesium, and drying to obtain carboxylated porous nano-silicon A;
wherein, the molar ratio of magnesium: 1 is silicon dioxide (2-4);
(2) preparing a graphene-doped silicon-carbon composite material:
preparing a catalyst organic solution with the mass concentration of (1-5) wt%, adding carboxylic acid porous nano-silicon A, uniformly dispersing, filtering, drying, transferring to a tubular furnace, heating to 600-1000 ℃ under a carbon source gas by a vapor deposition method, and keeping the temperature for 1-6 h to grow graphene on the surface of the catalyst organic solution to obtain a graphene doped silicon-carbon composite material;
mass ratio, catalyst: porous material A ═ (0.5-2): 100, respectively;
(3) preparing a lithium salt-coated graphene-doped silicon-carbon composite material:
then, embedding lithium salt into the surface layer of the graphene-doped silicon-carbon composite material through high-speed particle beam bombardment; the parameters of the particle injection method are that the particle injection is carried out in an oxygen atmosphere, the gas flow is (1-10) sccm, and the gas pressure is (1-10) × 10-4The injection temperature is 100 to-500 ℃ under Pa, and the time is 10 to 120 min; and obtaining the lithium salt-coated graphene-doped silicon-carbon composite material.
The catalyst organic flux in the step (2) is one or more of N-ethyl-5-methyl-2- (1-methylethyl) cyclohexanecarboxamide, N-butylbenzenesulfonamide, 3-amino-2, 2-dimethylpropionamide, erucamide N, N-diethyl-2-chloroacetamide, 2, 4-dihydroxybenzamide, 4-methoxybenzamide, N, N-ethylene bis-stearamide, valeramide, 2-hydroxyisobutyramide, N-methyl-p-toluenesulfonamide, N-phenylmaleimide, cinnamamide and cyclopropanesulfonamide;
the catalyst in the step (2) is one of ferric chloride, nickel chloride, cobalt chloride, ferric nitrate and nickel nitrate;
the lithium salt in the step (3) is one of lithium zirconate, lithium metaaluminate, lithium titanate and lithium niobate.
Has the advantages that:
1) the carboxylic acid nano silicon and the alkaline organic flux of the catalyst are adopted for chemical reaction, chemical groups such as amino groups are grafted on the surface of the nano silicon through chemical bonds, a network structure is formed, and the structural stability of the material is improved. Meanwhile, the catalyst can be firmly and uniformly doped on the surface of the nano silicon, and by taking the nano silicon as a matrix, graphene grows on the surface of the catalyst and vertically grows on the surface of the nano silicon, so that the expansion of the nano silicon is reduced, and the graphene vertical to the nano silicon is beneficial to the embedding of lithium ions and the promotion of the quick charging performance.
2) Lithium salt is deposited on the surface of the graphene-doped nano silicon by a particle injection method, so that the coating uniformity of the silicon-carbon material can be improved, the binding force between the graphene and the lithium salt is improved, the cycle performance of the material is improved, and the expansion of the material in the cycle process is reduced.
Drawings
Fig. 1 is an SEM image of the lithium salt-coated graphene-doped silicon-carbon composite material prepared in example 1;
Detailed Description
Example 1
(1) Preparation of carboxylated porous nano-silicon A:
grinding 72g of magnesium metal and 60g of silicon dioxide in a high-speed grinding machine for 24 hours, transferring the ground materials into a tubular furnace, heating the ground materials to 500 ℃ under the atmosphere of argon gas, carrying out thermal reduction for 24 hours, adding the ground materials into 500ml of 32 wt% nitric acid solution, soaking the solution for 24 hours for acid washing, removing the magnesium metal, and carrying out vacuum drying at 80 ℃ to obtain carboxylated porous nano-silicon A;
(2) preparing a graphene-doped silicon-carbon composite material:
adding 3g of ferric chloride into 100ml of N-ethyl-5-methyl-2- (1-methylethyl) cyclohexanecarboxamide organic solvent to prepare a catalyst organic solution with the mass concentration of 3 wt%, then adding 200g of porous silicon A, uniformly dispersing, filtering, drying, transferring to a tubular furnace, heating to 800 ℃ under methane carbon source gas by a vapor deposition method, and keeping the temperature for 3 hours to grow graphene on the surface of the porous silicon A, so as to obtain a graphene-doped silicon-carbon composite material;
(3) preparing a lithium salt-coated graphene-doped silicon-carbon composite material:
then, through high-speed particle beam bombardment, lithium zirconate is embedded into the surface layer of the graphene doped silicon-carbon composite material; the parameters of the particle injection method are that the particle injection is carried out in an oxygen atmosphere, the gas flow is 5sccm, and the gas pressure is 5 multiplied by 10-4Injecting at 300 deg.C under Pa for 60 min; and obtaining the lithium salt-coated graphene-doped silicon-carbon composite material.
Example 2
(1) Preparation of carboxylated porous nano-silicon A:
grinding 48g of metal magnesium and 60g of silicon dioxide in a high-speed grinding machine for 1h, transferring the ground materials into a tubular furnace, heating the ground materials to 600 ℃ under the atmosphere of argon gas, carrying out thermal reduction for 1h, adding the ground materials into 500ml of 32 wt% nitric acid solution, soaking the solution for 24h, carrying out acid washing, removing the metal magnesium, and carrying out vacuum drying at 80 ℃ to obtain carboxylated porous nano-silicon A;
(2) preparing a graphene-doped silicon-carbon composite material:
adding 1g of cobalt chloride into 100ml of 3-amino-2, 2-dimethylpropionamide organic solvent to prepare a catalyst organic solution with the mass concentration of 1 wt%, then adding 200g of porous silicon A, uniformly dispersing, filtering, drying, transferring to a tubular furnace, heating to 600 ℃ under acetylene carbon source gas by a vapor deposition method, and keeping the temperature for 6 hours to grow graphene on the surface of the porous silicon A, thereby obtaining the graphene doped silicon-carbon composite material;
(3) preparing a lithium salt-coated graphene-doped silicon-carbon composite material:
then, embedding lithium metaaluminate into the surface layer of the graphene doped silicon-carbon composite material through high-speed particle beam bombardment; the parameters of the particle injection method are that the particle injection is carried out in an oxygen atmosphere, the gas flow is 1sccm, and the gas pressure is 1 multiplied by 10-4Injecting at 500 deg.C under Pa for 10 min; and obtaining the lithium salt-coated graphene-doped silicon-carbon composite material.
Example 3
(1) Preparation of carboxylated porous nano-silicon A:
grinding 96g of metal magnesium and 60g of silicon dioxide in a high-speed grinding machine for 48 hours, then transferring to a tubular furnace, heating to 400 ℃ under the atmosphere of argon gas, carrying out thermal reduction for 48 hours, then adding to 500ml of 32 wt% nitric acid solution, soaking for 24 hours for acid washing, removing the metal magnesium, and carrying out vacuum drying at 80 ℃ to obtain carboxylated porous nano-silicon A;
(2) preparing a graphene-doped silicon-carbon composite material:
adding 5g of nickel nitrate into 100ml of N, N-diethyl-2-chloroacetamide organic solvent to prepare a catalyst organic solution with the mass concentration of 5 wt%, then adding 250g of porous silicon A, uniformly dispersing, filtering, drying, transferring to a tubular furnace, heating to 1000 ℃ under ethylene carbon source gas by a vapor deposition method, and keeping the temperature for 1h to grow graphene on the surface of the material to obtain the graphene doped silicon-carbon composite material;
(3) preparing a lithium salt-coated graphene-doped silicon-carbon composite material:
then, embedding lithium niobate into the surface layer of the graphene doped silicon-carbon composite material through high-speed particle beam bombardment; the parameters of the particle injection method are that the particle injection is carried out in an oxygen atmosphere, the gas flow is 10sccm, and the gas pressure is 10 multiplied by 10-4Injecting at 100 deg.C under Pa for 120 min; and obtaining the lithium salt-coated graphene-doped silicon-carbon composite material.
Comparative example 1:
adding 3g of ferric chloride into 100ml of N-ethyl-5-methyl-2- (1-methylethyl) cyclohexanecarboxamide organic solvent to prepare a catalyst organic solution with the mass concentration of 3 wt%, then adding 200g of nano-silicon, uniformly dispersing, filtering, drying, transferring to a tubular furnace, heating to 800 ℃ under methane carbon source gas by a vapor deposition method, and keeping the temperature for 3 hours to grow graphene on the surface of the carbon, thereby obtaining the graphene doped silicon-carbon composite material;
comparative example 2:
embedding lithium niobate into the surface layer of the nano-silicon by high-speed particle beam bombardment; the parameters of the particle injection method are that the particle injection is carried out in an oxygen atmosphere, the gas flow is 10sccm, and the gas pressure is 10 multiplied by 10-4Injecting at 100 deg.C under Pa for 120 min; and obtaining the lithium salt coated nano silicon composite material.
(1) Topography testing
SEM test was performed on the lithium salt-coated graphene-doped silicon carbon composite material in example 1, and the test results are shown in fig. 1. As can be seen from FIG. 1, the material has a spherical structure, and the particle size distribution of the material is uniform and reasonable, the particle diameter of the material is between 5-20 μm, wherein D50 is 12.0 μm, the inner core is 10 μm, and the outer shell is 2 μm.
(2) Button cell test
The composite materials in examples 1-3 and comparative examples 1-2 are used as negative electrode materials of lithium ion batteries to assemble button batteries, which are respectively marked as A1, A2, A3, B1 and B2.
The preparation method comprises the following steps: adding a binder, a conductive agent and a solvent into a lithium ion battery negative electrode material, stirring and pulping, coating the mixture on copper foil, and drying and rolling to prepare a negative electrode plate; the binder is LA132, the conductive agent is SP, the solvent is NMP, and the dosage ratio of the negative electrode material, SP, PVDF and NMP is 95 g: 1 g: 4 g: 220 mL; LiPF in electrolyte6A mixture of EC and DEC with a volume ratio of 1:1 is used as an electrolyte; the metal lithium sheet is a counter electrode, and the diaphragm is a polypropylene (PP) film. Button cell assembly was performed in an argon-filled glove box. The electrochemical performance is carried out on a Wuhan blue electricity CT2001A type battery tester, the charging and discharging voltage range is 0.005V to 2.0V, and the charging and discharging rate is 0.1C.
The test results are shown in table 1.
TABLE 1
As can be seen from the data in table 1, the specific capacity and the first efficiency of the lithium salt-coated graphene-doped silicon-carbon composite material prepared in the embodiment of the present invention are significantly better than those of comparative examples 1 and 2. The reason may be that lithium salt with high density is deposited on the surface of the graphene/nano silicon by a high-speed particle beam bombardment method to provide sufficient lithium ions to reduce the loss of irreversible lithium ions in the charging and discharging processes, so as to improve the primary efficiency, and meanwhile, the lithium salt coated on the surface by a particle method has high density to isolate the contact between the electrolyte and the core, so as to reduce the occurrence of side reactions and improve the primary efficiency; meanwhile, the nano silicon structure with the porous inner core has a high specific surface area, and graphene can firmly grow on the surface of the nano silicon structure to improve the powder conductivity of the material.
(3) Testing the soft package battery:
the negative electrode sheet was prepared by doping 90% of the artificial graphite as a negative electrode material with the composite materials of examples 1 to 3 and comparative examples 1 and 2, and N was usedCM532 is positive electrode material; LiPF in electrolyte6A mixture of EC and DEC with a volume ratio of 1:1 is used as an electrolyte; 5Ah pouch cells, labeled C1, C2, C3, D1, and D2, were prepared with Celgard 2400 membrane as the separator. And respectively testing the liquid absorption and retention capacity, the pole piece rebound, the pole piece resistivity and the cycle performance of the negative pole piece.
a. Imbibition ability test
And (3) adopting a 1mL burette, sucking the electrolyte VmL, dripping a drop on the surface of the pole piece, timing until the electrolyte is completely absorbed, recording the time t, and calculating the liquid absorption speed V/t of the pole piece. The test results are shown in table 2.
b. Liquid retention test
Calculating the theoretical liquid absorption amount m of the pole piece according to the pole piece parameters1And weighing the weight m of the pole piece2Then, the pole piece is placed in electrolyte to be soaked for 24 hours, and the weight of the pole piece is weighed to be m3Calculating the amount m of the pole piece liquid absorption3-m2And calculated according to the following formula: retention rate ═ m3-m2) 100%/m 1. The test results are shown in table 2.
TABLE 2
As can be seen from table 2, the liquid absorption and retention capacities of the lithium salt-coated graphene-doped silicon carbon composite materials obtained in examples 1 to 3 are significantly higher than those of comparative examples 1 and 2. Experimental results show that the lithium salt-coated graphene doped silicon-carbon composite material has high liquid absorption and retention capacity. The reason for this may be: the specific surface of the composite material of the embodiment is larger, so that the liquid absorption and retention capacity of the material is improved.
c. Pole piece rebound rate test
Firstly, testing the average thickness of a pole piece to be D1 by using a thickness gauge, then placing the pole piece in a vacuum drying oven of 80 ℃ for drying for 48h, testing the thickness of the pole piece to be D2, and calculating according to the following formula: the rebound rate was (D2-D1) × 100%/D1. The test results are shown in table 3.
d. Pole piece resistivity testing
The resistivity of the pole piece was measured using a resistivity tester, and the results are shown in table 3.
TABLE 3
As can be seen from the data in table 3, the rebound rate of the negative electrode sheet prepared from the lithium salt coated graphene doped silicon carbon composite material obtained in examples 1 to 3 is significantly lower than that of the negative electrode sheets prepared from comparative examples 1 and 2, that is, the negative electrode sheet prepared from the lithium salt coated graphene or silicon carbon composite material of the present invention has a lower rebound rate. The reason for this may be: the expansion of the porous silicon structure of the inner core is reduced, and meanwhile, the lithium salt deposited by the particle method has high density and restrains the expansion of lithium ions in the charging and discharging processes to reduce the expansion; meanwhile, the powder of the embodiment has high conductivity, so that the resistivity of the pole piece is reduced.
e. Cycle performance test
The cycle performance of the battery is tested at the temperature of 25 +/-3 ℃ with the charge-discharge multiplying power of 1C/1C and the voltage range of 2.5V-4.2V. The test results are shown in table 4.
TABLE 4
As can be seen from table 4, the cycle performance of the battery prepared from the lithium salt-coated graphene doped silicon carbon composite material of the present invention is significantly better than that of the comparative example, and the reason for this is probably that the electrode plate prepared from the lithium salt-coated graphene doped silicon carbon composite material of the present invention has a lower expansion rate, the structure of the electrode plate is more stable during the charging and discharging processes, and the cycle performance is improved. In addition, the lithium salt coated on the surface of the lithium salt-coated graphene doped silicon-carbon composite material has the characteristics of high density and strong structural stability, so that the cycle performance of the lithium salt-coated graphene doped silicon-carbon composite material is improved.
Claims (6)
1. The lithium salt-coated graphene-doped silicon-carbon composite material is characterized in that the silicon-carbon negative electrode material is of a core-shell structure, the inner core is graphene-doped nano-silicon, the outer shell is lithium salt, and the mass ratio of the outer layer is (1-10) wt%.
2. The lithium salt-coated graphene-doped silicon-carbon composite material as claimed in claim 1, wherein the mass ratio of graphene to nano-silicon in the core is (1-5): (95-99).
3. The method for preparing the lithium salt-coated graphene-doped silicon-carbon composite material according to claim 1, comprising the following steps:
(1) preparation of carboxylated porous nano-silicon A:
grinding metal magnesium and silicon dioxide in a high-speed grinding machine for 1-48 h, transferring the ground metal magnesium and silicon dioxide into a tubular furnace, heating to 400-600 ℃ in an argon atmosphere for thermal reduction for 1-48 h, adding the obtained product into a nitric acid solution, soaking and pickling to remove the metal magnesium, and drying to obtain carboxylated porous nano-silicon A;
wherein, the molar ratio of magnesium: 1 is silicon dioxide (2-4);
(2) preparing a graphene-doped silicon-carbon composite material:
preparing a catalyst organic solution with the mass concentration of (1-5) wt%, adding porous silicon A, uniformly dispersing, filtering, drying, transferring to a tubular furnace, heating to 600-1000 ℃ under a carbon source gas by a vapor deposition method, and keeping the temperature for 1-6 h to grow graphene on the surface of the catalyst organic solution to obtain a graphene doped silicon-carbon composite material;
mass ratio, catalyst: porous material A ═ (0.5-2): 100, respectively;
(3) preparing a lithium salt-coated graphene-doped silicon-carbon composite material:
then, embedding lithium salt into the surface layer of the graphene-doped silicon-carbon composite material through high-speed particle beam bombardment; the above-mentionedThe parameters of the particle implantation method are that the method is performed in an oxygen atmosphere, the gas flow is (1-10) sccm, and the gas pressure is (1-10) × 10-4The injection temperature is 100-500 ℃ under Pa, and the time is 10-120 min; and obtaining the lithium salt-coated graphene-doped silicon-carbon composite material.
4. The method of preparing the lithium salt-coated graphene doped silicon carbon composite material according to claim 3, wherein the organic solvent of the catalyst in the step (2) is one or more of N-ethyl-5-methyl-2- (1-methylethyl) cyclohexanecarboxamide, N-butylbenzenesulfonamide, 3-amino-2, 2-dimethylpropionamide, erucamide N, N-diethyl-2-chloroacetamide, 2, 4-dihydroxybenzamide, 4-methoxybenzamide, N, N-ethylenebisstearamide, valeramide, 2-hydroxyisobutyramide, N-methyl-p-toluenesulfonamide, N-phenylmaleimide, cinnamamide, and cyclopropanesulfonamide.
5. The method for preparing the lithium salt-coated graphene-doped silicon-carbon composite material according to claim 3, wherein the catalyst in the step (2) is one of ferric chloride, nickel chloride, cobalt chloride, ferric nitrate and nickel nitrate.
6. The method for preparing a lithium salt-coated graphene-doped silicon-carbon composite material according to claim 3, wherein the lithium salt in the step (3) is one of lithium zirconate, lithium metaaluminate, lithium titanate and lithium niobate.
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