CN115954465B - High-power hard carbon composite material and preparation method thereof - Google Patents
High-power hard carbon composite material and preparation method thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 11
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion battery materials, and provides a high-power hard carbon composite material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, adding resin into organic alcohol for dissolution, and then adding inorganic ferric salt to obtain suspension A; s2, adding ammonia fluoride into the graphene oxide solution, and uniformly dispersing to obtain a solution B; s3, adding the solution B into the suspension A, heating to 50-100 ℃, adding a cross-linking agent, and introducing oxidizing gas to obtain a mixture C; s4, drying and carbonizing the mixture C to obtain the high-power hard carbon composite material. Through the technical scheme, the problems of poor power performance, first efficiency and cycle performance of hard carbon in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a high-power hard carbon composite material and a preparation method thereof.
Background
Carbon materials are a necessary choice for negative electrode materials due to their abundant reserves, excellent conductivity and good cycling stability. Carbon materials can be generally classified into graphite materials (natural graphite and modified graphite) and amorphous carbon hard carbon and soft carbon according to the difference in graphitization degree of the carbon materials.
The hard carbon material is applied to the fields of HEVs and the like due to the advantages of low expansion, excellent low-temperature performance, wide material sources and the like, but the first low efficiency and normal-temperature power performance deviation limit the popularization and application of the hard carbon material in the fields of EV and the like.
The method for improving the first efficiency of the material is that the surface of the material is coated with soft carbon, and the first efficiency can improve but can reduce the power performance of the material; if the power performance of the material can be improved by reducing the particle size or doping with a metal element, the energy density can be reduced. Therefore, by means of doping, cladding and other measures, the energy density, the first efficiency and the power performance of the material can be improved.
Disclosure of Invention
The invention provides a high-power hard carbon composite material and a preparation method thereof, which solve the problems of poor power performance, first efficiency and cycle performance of hard carbon in the prior art.
The technical scheme of the invention is as follows:
the preparation method of the high-power hard carbon composite material comprises the following steps:
s1, adding resin into organic alcohol for dissolution, and then adding inorganic ferric salt to obtain suspension A;
s2, adding ammonia fluoride into the graphene oxide solution, and uniformly dispersing to obtain a solution B;
s3, adding the solution B into the suspension A, heating to 50-100 ℃, adding a cross-linking agent, and introducing oxidizing gas to obtain a mixture C;
s4, drying and carbonizing the mixture C to obtain the high-power hard carbon composite material.
As a further technical scheme, the resin comprises one or more of epoxy resin, phenolic resin and furfural resin.
As a further technical scheme, the organic alcohol comprises one or more of butanediol, ethylene glycol, glycerol, n-butanol and benzyl alcohol.
As a further technical scheme, the valence of iron in the inorganic ferric salt is trivalent.
As a further technical scheme, the inorganic ferric salt is one or more of ferric sulfate, ferric nitrate and ferric chloride.
As a further technical scheme, the mass ratio of the resin, the organic alcohol and the inorganic ferric salt is 100:500-2000:1-10.
As a further technical scheme, the method also comprises at least one of the following technical characteristics:
the graphene oxide solution is an N-methylpyrrolidone solution of graphene oxide;
the concentration of the graphene oxide is 1-5wt%;
the mass ratio of the ammonia fluoride to the graphene oxide is 1-10:0.5-2.
As a further technical scheme, the method also comprises at least one of the following technical characteristics:
the mass ratio of the cross-linking agent to the resin is 5-20:100;
the cross-linking agent is one of furfural, benzaldehyde, trioxymethylene and formaldehyde.
As a further technical scheme, the oxidizing gas is one of chlorine, bromine, oxygen and hydrogen peroxide.
As a further technical scheme, the addition amounts of the suspension A and the solution B are as follows: fe (Fe) 3+ And F is equal to - The molar ratio of (2) is 1:1-5.
As a further technical scheme, the carbonization temperature is 800-1200 ℃ and the time is 1-6h.
As a further technical scheme, the airflow rate of the oxidizing gas is 10-100mL/min, and the introducing time is 30-300min.
The high-power hard carbon composite material is prepared according to the preparation method and consists of hard carbon and ferric fluoride doped between the hard carbon and the ferric fluoride, wherein the mass ratio of the ferric fluoride accounts for 1-10wt% of the total amount of the composite material.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the ferric fluoride is doped in the hard carbon, on one hand, the specific capacity and high electronic conductivity of the ferric fluoride are utilized, the impedance is reduced, and on the other hand, the ferric fluoride has better compatibility with electrolyte, and the high-temperature storage performance can be improved.
2. Inorganic ferric salt is uniformly mixed in a hard carbon precursor by adopting a liquid phase method, so that impedance is reduced; meanwhile, fluoride is doped in the graphene oxide solution, and aggregation of fluoride is avoided by means of a lamellar structure of graphene; meanwhile, the surface treatment is carried out by adding the cross-linking agent and the oxidizing gas, so that holes are formed in the hard carbon to improve the lithium storage capacity, and the defects on the surface of the material are reduced by the oxidizing gas, so that the first efficiency is improved.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is an SEM image of an iron fluoride doped hard carbon composite material prepared according to example 1.
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 one of ordinary skill 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 preparation method of the high-power hard carbon composite material comprises the following steps:
s1, adding 100g of phenolic resin into 1000g of glycerol for dissolution, and then adding 5g of ferric sulfate (0.0125 mol) to obtain a suspension A;
s2, adding 1.85g of ammonia fluoride (0.05 mol) into 40g of N-methylpyrrolidone solution of graphene oxide with concentration of 3wt% to uniformly disperse to obtain solution B;
s3, adding the solution B obtained in the step S2 into the suspension A obtained in the step S1, heating to 80 ℃, stirring for 3 hours, adding 10g of furfural, introducing chlorine gas with the air flow rate of 50mL/min for 60min, and filtering to obtain a mixture C;
s4, drying the mixture C at 80 ℃ in vacuum for 24 hours, and carbonizing at 900 ℃ for 3 hours to obtain the ferric fluoride doped hard carbon composite material.
Example 2
The preparation method of the high-power hard carbon composite material comprises the following steps:
s1, adding 100g of furfural resin into 500g of glycerol for dissolution, and then adding 1g of ferric nitrate (0.0041 mol) to obtain suspension A;
s2, adding 0.7585g of ammonia fluoride (0.0205 mol) into 37.9g of 1wt% graphene oxide N-methylpyrrolidone solution, and uniformly dispersing to obtain a solution B;
s3, adding the solution B obtained in the step S2 into the suspension A obtained in the step S1, heating to 50 ℃, stirring for 3 hours, adding 5g of benzaldehyde, introducing bromine gas, wherein the air flow rate is 10mL/min, the introducing time is 300min, and filtering to obtain a mixture C;
s4, drying the mixture C at 80 ℃ in vacuum for 24 hours, and carbonizing at 800 ℃ for 6 hours to obtain the ferric fluoride doped hard carbon composite material.
Example 3
The preparation method of the high-power hard carbon composite material comprises the following steps:
s1, adding 100g of epoxy resin into 2000g of benzyl alcohol for dissolution, and then adding 10g of ferric chloride (0.062 mol) to obtain a suspension A;
s2, adding 6.85g of ammonia fluoride (0.186 mol) into 40g of N-methylpyrrolidone solution of graphene oxide with concentration of 5wt% to disperse uniformly to obtain solution B;
s3, adding the solution B obtained in the step S2 into the suspension A obtained in the step S1, heating to 100 ℃, stirring for 3 hours, adding 20g of trioxymethylene, introducing oxygen gas, wherein the air flow rate is 100mL/min, the introducing time is 30min, and filtering to obtain a mixture C;
s4, drying the mixture C at 80 ℃ in vacuum for 24 hours, and carbonizing at 1200 ℃ for 1 hour to obtain the ferric fluoride doped hard carbon composite material.
Comparative example 1
100g of phenolic resin, 10g of 1wt% graphene oxide N-methyl pyrrolidone solution are stirred for 3 hours at the temperature of 80 ℃,10g of furfural is added and stirred for 3 hours, then filtration and vacuum drying are carried out at the temperature of 80 ℃, and the obtained material is transferred into a tubular furnace and carbonized for 3 hours at the temperature of 900 ℃ to obtain the graphene doped hard carbon composite material.
Comparative example 2
The preparation method of the high-power hard carbon composite material comprises the following steps:
s1, adding 100g of phenolic resin into 1000g of glycerol for dissolution, and then adding 5g of ferric sulfate (0.0125 mol) to obtain a suspension A;
s2, adding 1.85g of ammonia fluoride (0.05 mol) into the suspension A obtained in the step S1, heating to 80 ℃, stirring for 3 hours, adding 10g of furfural, introducing chlorine gas with the gas flow rate of 50mL/min for 60min, and filtering to obtain a mixture C;
s3, drying the mixture C at 80 ℃ in vacuum for 24 hours, and carbonizing at 900 ℃ for 3 hours to obtain the ferric fluoride doped hard carbon composite material.
Comparative example 3
The preparation method of the high-power hard carbon composite material comprises the following steps:
s1, adding 100g of phenolic resin into 1000g of glycerol for dissolution, and then adding 5g of ferric sulfate (0.0125 mol) to obtain a suspension A;
s2, adding 1.85g of ammonia fluoride (0.05 mol) into 40g of N-methylpyrrolidone solution of graphene oxide with concentration of 3wt% to uniformly disperse to obtain solution B;
s3, adding the solution B obtained in the step S2 into the suspension A obtained in the step S1, uniformly stirring, introducing chlorine gas, wherein the air flow rate is 50mL/min, the introducing time is 60min, and filtering to obtain a mixture C;
s4, drying the mixture C at 80 ℃ in vacuum for 24 hours, and carbonizing at 900 ℃ for 3 hours to obtain the ferric fluoride doped hard carbon composite material.
Comparative example 4
The ammonia fluoride was replaced with an equimolar amount of sodium fluoride as compared to example 1, and the other steps were the same as in example 1.
The testing method comprises the following steps:
1. SEM test
SEM test is carried out on the iron fluoride doped hard carbon composite material prepared in the embodiment 1, and the result is shown in fig. 1, and it can be seen from the graph that the hard carbon material prepared in the embodiment 1 has a spheroid-like structure, uniform size distribution and particle size of 5-15 mu m.
2. Physical and chemical properties and button cell testing
The hard carbon composites prepared in examples and comparative examples were subjected to particle size, tap density, specific surface area, elemental analysis, and specific capacity tests. The testing method comprises the following steps: GB/T-24533-2019 lithium ion battery graphite cathode material.
The hard carbon composites obtained in examples 1 to 3 and comparative example were assembled into button cells A1, A2, A3, respectivelyB1; the preparation method comprises the following steps: adding binder, conductive agent and solvent into the cathode material, stirring to slurry, coating on copper foil, oven drying, and rolling. The binder is LA132 binder, the conductive agent SP, the negative electrode material is hard carbon material prepared in the examples and comparative examples, the solvent is secondary distilled water, and the proportion is: negative electrode material: SP: LA132: secondary distilled water = 95g:1g:4g:220mL, and preparing a negative pole piece; the electrolyte is LiPF 6 EC+DEC (volume ratio 1:1, concentration 1.3 mol/L), the metal lithium sheet is a counter electrode, the diaphragm adopts polyethylene PE, the simulated battery is assembled in a glove box filled with argon, the electrochemical performance is carried out on a Wuhan blue electric CT2001A type battery tester, the charging and discharging voltage range is 0.00V to 2.0V, and the charging and discharging rate is 0.1C. The button cell was also tested for its rate (2C/0.1C) and cycle performance (0.2C/0.2C, 200 times) and the test results are shown in Table 1.
Table 1 physicochemical properties of the composite materials obtained in examples and comparative examples and results of button cell test
As can be seen from table 1, the first discharge capacity and first efficiency, rate capability and cycle performance of the hard carbon composite material prepared in the examples were significantly improved as compared with the comparative examples, because the hard carbon composite material according to the present invention contains ferric fluoride and has a reduced resistance to improve rate capability by virtue of its high specific capacity and high electron conductivity. Meanwhile, by means of adding the cross-linking agent and oxidizing gas surface treatment, holes are formed in the hard carbon to improve the lithium storage capacity, and by means of oxidizing gas, defects on the surface of the material are reduced, so that the first efficiency is improved.
3. High temperature storage performance test of the soft package battery:
the hard carbon composite materials of examples and comparative examples were used as negative electrodes, and a negative electrode sheet was prepared by slurry mixing and coating, using a ternary material (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) As positive electrode, with LiPF 6 (the solvent is EC+DEC, volume ratio)1:1, electrolyte concentration 1.1 mol/L) is used as electrolyte, and Celgard2400 membrane is used as a diaphragm to prepare the 2Ah soft-package battery.
The capacity of the battery under the full-charge state is tested to be X at 60 DEG C 1 After 30 days of standing at 60 ℃, the battery was tested again for capacity X 2 Charge retention=x was calculated 2 /X 1 *100%; after that, after the battery is fully charged to a full state (100% SOC), the capacity of the battery is tested to be X 3 Recovery capacity=x is calculated 3 /X 1 *100%; the results are shown in Table 2.
Table 2 test of high temperature storage performance of the composite materials of examples and comparative examples for preparing soft pack batteries
As can be seen from table 2, the high temperature storage performance of the example material is superior to that of the comparative example, because the ferric fluoride has better compatibility with the electrolyte, and the high temperature storage performance is improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. The preparation method of the high-power hard carbon composite material is characterized by comprising the following steps of:
s1, adding resin into organic alcohol for dissolution, and then adding inorganic ferric salt to obtain suspension A;
s2, adding ammonia fluoride into the graphene oxide solution, and uniformly dispersing to obtain a solution B;
s3, adding the solution B into the suspension A, heating to 50-100 ℃, adding a cross-linking agent, and introducing oxidizing gas to obtain a mixture C;
s4, drying and carbonizing the mixture C to obtain a high-power hard carbon composite material;
the resin comprises one or more of epoxy resin, phenolic resin and furfural resin;
the inorganic ferric salt is one or more of ferric sulfate, ferric nitrate and ferric chloride;
the mass ratio of the cross-linking agent to the resin is 5-20:100;
the cross-linking agent is one of furfural, benzaldehyde, trioxymethylene and formaldehyde.
2. The method for preparing the high-power hard carbon composite material according to claim 1, wherein the mass ratio of the resin to the organic alcohol to the inorganic ferric salt is 100:500-2000:1-10.
3. The method for preparing a high-power hard carbon composite material according to claim 1, further comprising at least one of the following technical features:
the graphene oxide solution is an N-methylpyrrolidone solution of graphene oxide;
the concentration of the graphene oxide is 1-5wt%;
the mass ratio of the ammonia fluoride to the graphene oxide is 1-10:0.5-2.
4. The method for preparing a high-power hard carbon composite material according to claim 1, wherein the oxidizing gas is one of chlorine, bromine, oxygen and hydrogen peroxide.
5. The method for preparing the high-power hard carbon composite material according to claim 1, wherein the addition amounts of the suspension A and the solution B are as follows: fe (Fe) 3+ And F is equal to - The molar ratio of (2) is 1:1-5.
6. A high power hard carbon composite material, characterized in that it is obtained according to the preparation method of any one of claims 1-5, consisting of hard carbon and iron fluoride doped between them, the mass ratio of iron fluoride being 1-10% by weight of the total amount of the composite material.
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Effective date of registration: 20231222 Address after: 653100 Longquan District, high tech Zone, Yuxi City, Yunnan Province (Sanjie community, Dajie street, Jiangchuan District) Patentee after: Yunnan Kuntian New Energy Co.,Ltd. Address before: 050000 No. 8, kuntian Avenue, Suyang Township, Yuanshi County, Shijiazhuang City, Hebei Province Patentee before: Hebei kuntian new energy Co.,Ltd. |