CN117542977B - Hard carbon composite material prepared by electrochemical deposition method and preparation method thereof - Google Patents
Hard carbon composite material prepared by electrochemical deposition method and preparation method thereof Download PDFInfo
- Publication number
- CN117542977B CN117542977B CN202311547998.2A CN202311547998A CN117542977B CN 117542977 B CN117542977 B CN 117542977B CN 202311547998 A CN202311547998 A CN 202311547998A CN 117542977 B CN117542977 B CN 117542977B
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- sodium
- composite material
- preparing
- carbon composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 133
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000006260 foam Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 50
- 239000007833 carbon precursor Substances 0.000 claims description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- 238000003763 carbonization Methods 0.000 claims description 23
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 20
- -1 ether compound Chemical class 0.000 claims description 20
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 19
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 19
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 14
- 238000010000 carbonizing Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910019398 NaPF6 Inorganic materials 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021260 NaFe Inorganic materials 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000674 effect on sodium Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of secondary batteries, and provides a method for preparing a hard carbon composite material by an electrochemical deposition method, wherein the hard carbon composite material consists of a core and a shell; the inner core consists of hard carbon, sodium doped amorphous carbon and foam nickel, and the outer shell is inorganic sodium salt. Through the technical scheme, the problem that the first efficiency is low when the hard carbon material in the prior art is applied to the sodium ion battery is solved.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a hard carbon composite material prepared by an electrochemical deposition method and a preparation method thereof.
Background
Hard carbon materials are low graphitization materials with large interlayer spacing and structural stability, but the specific capacity and the first efficiency of the current commercialized hard carbon materials are low, which limits the application of the hard carbon materials in batteries.
The hard carbon material is used as a key material of a negative electrode material of a sodium ion battery, the preparation method is mainly prepared by a solid phase method, a hard carbon precursor and a cross-linking agent are prepared into the hard carbon material through solid phase sintering carbonization, the consistency is poor, the first efficiency of the hard carbon material is low due to a plurality of defects on the surface of the hard carbon material, meanwhile, the specific capacity of the hard carbon is larger in relation with the sintering temperature of the hard carbon material, the specific capacity deviation of the hard carbon material is larger due to the temperature difference, and the sintering period is long. The electrochemical method has the advantages of controllable process, controllable deposition thickness and high deposition efficiency, and can deposit different materials according to performance requirements, thereby realizing the functional requirements of the materials. Although patent application CN202310081306.3 discloses a hard carbon composite material for lithium ion battery and a preparation method thereof, a gas atomization method is adopted, hard carbon is used as a matrix, silicon phosphate is deposited in pores of the hard carbon for filling, then organic lithium salt is deposited on the surface of the hard carbon by an electrochemical deposition method, so as to obtain a phosphorus-silicon doped hard carbon composite material, the composite material of the hard carbon composite material improves the first efficiency and the power performance thereof by shell lithium salt deposition, but the composite material can form an alloy with lithium, but can not form an alloy with sodium to provide capacity, so the hard carbon composite material can only be applied to lithium ion batteries, but has no effect on sodium ion batteries.
Disclosure of Invention
The invention provides a hard carbon composite material prepared by an electrochemical deposition method and a preparation method thereof, which solve the problem of low first efficiency of the hard carbon material applied to sodium ion batteries in the related technology.
The technical scheme of the invention is as follows:
The invention provides a method for preparing a hard carbon composite material by electrochemical deposition, wherein the hard carbon composite material consists of a core and a shell; the inner core consists of hard carbon, sodium-doped amorphous carbon and foam nickel, and the outer shell is inorganic sodium salt.
As a further technical scheme, the inorganic sodium salt is one of sodium hexafluorophosphate, sodium trifluoromethanesulfonate, sodium tetrachloroborate, sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroantimonate, sodium benzoate, sodium p-toluenesulfonate, sodium difluorosulfimide, sodium tetrachloroaluminate, sodium tetrachloroferrite and sodium tetraphenylboron.
The invention also provides a preparation method for preparing the hard carbon composite material by using the electrochemical deposition method, which comprises the following steps:
s1, preparing a hard carbon precursor material: performing ball milling mixing on phenolic resin after first carbonization and diethyl ether, curing, crushing and performing second carbonization to obtain a hard carbon precursor material;
S2, preparing a hard carbon precursor/foam nickel material: mixing the hard carbon precursor material and sodium carboxymethylcellulose, and pressing the mixture on foam nickel to obtain a hard carbon precursor/foam nickel material;
s3, preparing a hard carbon composite material: and (3) taking the hard carbon precursor/foam nickel material as a working electrode, taking an ether compound containing inorganic sodium salt as a solvent, taking a saturated calomel electrode as a counter electrode, performing electrochemical deposition, washing, drying, and carbonizing for the third time to obtain the hard carbon composite material.
As a further technical scheme, the mass ratio of the phenolic resin to the diethyl ether in the S1 is 100:100-500.
As a further technical scheme, the mass ratio of the hard carbon precursor material to the sodium carboxymethyl cellulose in the S2 is 80:20-95:5.
As a further technical scheme, the molar concentration of the ether compound containing the inorganic sodium salt in the S3 is 0.5-1.5 mol/L.
As a further technical scheme, the temperature of the first carbonization in the step S1 is 800-1500 ℃, and the carbonization time is 1-6 h; the temperature during curing is 250-500 ℃, and the curing time is 1-6 hours; the temperature of the secondary carbonization is 800-1500 ℃, the carbonization time is 1-6 h, and the carbonization is performed under the protection of argon inert gas.
As a further technical scheme, the temperature in the third carbonization in the step S3 is 500-800 ℃, and the carbonization time is 1-6 h.
As a further technical scheme, the ether compound in the S3 is one of diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
As a further technical scheme, the electrochemical deposition in the step S3 adopts cyclic voltammetry, the scanning speed is 0.5-5 mV/S, the voltage range is-2V, and the scanning cycle number is 10-100 weeks.
The working principle and the beneficial effects of the invention are as follows:
1. In the invention, the hard carbon composite material adopts hard carbon, sodium doped amorphous carbon and foam nickel to form an inner core, and inorganic sodium salt to form an outer shell of the hard carbon material, has high conductivity, and has excellent first efficiency, rate characteristic, quick charge performance and high specific capacity when applied to a battery.
2. According to the invention, the sodium carboxymethyl cellulose is doped in the hard carbon precursor/foam nickel material, the proportion of the hard carbon precursor and the sodium carboxymethyl cellulose is regulated and controlled, and the sodium carboxymethyl cellulose is conveniently pressed on foam nickel by means of the self bonding function of the sodium carboxymethyl cellulose, so that the sodium salt is beneficial to electrochemical deposition, and meanwhile, sodium carboxymethyl cellulose forms sodium doped amorphous carbon after carbonization at high temperature, so that the first efficiency, the multiplying power performance and the quick charging performance of the hard carbon composite material are improved.
3. According to the invention, the inorganic sodium salt is deposited on the surface of the hard carbon through electrochemical deposition, so that the method has the advantages of high deposition density, controllable process, high deposition efficiency, and improvement of the first efficiency and quick charging performance of the hard carbon composite material after carbonization.
Drawings
FIG. 1 is an SEM image of a hard carbon composite material according to example 1 of the present invention.
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.
In the following examples and comparative examples, the model numbers (product numbers) and manufacturer information of the raw materials used are shown in table 1:
table 1 raw material information used in examples and comparative examples
Example 1
The preparation method for preparing the hard carbon composite material by using the electrochemical deposition method comprises the following steps:
S1, preparing a hard carbon precursor material: carbonizing 100g of phenolic resin at 800 ℃ for 6 hours, ball-milling and mixing with 300g of diethyl ether, solidifying at 350 ℃ for 3 hours, crushing, and carbonizing at 1200 ℃ for 3 hours under the protection of argon inert gas to obtain a hard carbon precursor material;
S2, preparing a hard carbon precursor/foam nickel material: mixing 90g of hard carbon precursor material and 10g of sodium carboxymethylcellulose, and pressing on the foam nickel to obtain a hard carbon precursor/foam nickel material;
S3, preparing a hard carbon composite material: taking a hard carbon precursor/foam nickel material as a working electrode, taking diethylene glycol dimethyl ether with the molar concentration of 1mol/L sodium hexafluorophosphate as a solvent, taking a saturated calomel electrode as a counter electrode, adopting a cyclic voltammetry, scanning at the scanning speed of 1mV/s, the voltage range of-2V to 2V, scanning for 50 weeks, deionizing and washing, vacuum drying at 80 ℃ for 24 hours, and carbonizing at 600 ℃ for 3 hours to obtain the hard carbon composite material.
Example 2
The preparation method for preparing the hard carbon composite material by using the electrochemical deposition method comprises the following steps:
S1, preparing a hard carbon precursor material: carbonizing 100g of phenolic resin at 1500 ℃ for 1h, ball-milling and mixing with 100g of diethyl ether, solidifying at 250 ℃ for 6h, crushing, and carbonizing at 800 ℃ for 6h under the protection of argon inert gas to obtain a hard carbon precursor material;
S2, preparing a hard carbon precursor/foam nickel material: mixing 90g of hard carbon precursor material and 10g of sodium carboxymethylcellulose, and pressing on the foam nickel to obtain a hard carbon precursor/foam nickel material;
S3, preparing a hard carbon composite material: taking a hard carbon precursor/foam nickel material as a working electrode, taking ethylene glycol dimethyl ether with the molar concentration of 0.5mol/L sodium triflate as a solvent, taking a saturated calomel electrode as a counter electrode, adopting a cyclic voltammetry, scanning at the scanning speed of 0.5mV/s and the voltage range of-2V to 2V, scanning for 10 weeks, deionizing and washing, vacuum drying at 80 ℃ for 24 hours, carbonizing at the temperature of 500 ℃ for 6 hours, and obtaining the hard carbon composite material.
Example 3
The preparation method for preparing the hard carbon composite material by using the electrochemical deposition method comprises the following steps:
S1, preparing a hard carbon precursor material: carbonizing 100g of phenolic resin at 1500 ℃ for 1h, ball-milling and mixing with 500g of diethyl ether, solidifying at 500 ℃ for 1h, crushing, and carbonizing at 1500 ℃ for 1h under the protection of argon inert gas to obtain a hard carbon precursor material;
S2, preparing a hard carbon precursor/foam nickel material: mixing 90g of hard carbon precursor material and 10g of sodium carboxymethylcellulose, and pressing on the foam nickel to obtain a hard carbon precursor/foam nickel material;
S3, preparing a hard carbon composite material: taking a hard carbon precursor/foam nickel material as a working electrode, taking triethylene glycol dimethyl ether with the molar concentration of 1.5mol/L sodium tetrachloroborate as a solvent, taking a saturated calomel electrode as a counter electrode, adopting a cyclic voltammetry, scanning at a scanning speed of 5mV/s and a voltage range of-2V, scanning for 100 weeks, deionizing and washing, vacuum drying at 80 ℃ for 24 hours, carbonizing at 800 ℃ for 1 hour, and obtaining the hard carbon composite material.
Example 4
This example differs from example 1 only in that 80g of hard carbon precursor material and 20g of sodium carboxymethylcellulose are added.
Example 5
This example differs from example 1 only in that 95g of hard carbon precursor material and 5g of sodium carboxymethylcellulose are added.
Example 6
This example differs from example 1 only in the addition of 70g of hard carbon precursor material and 30g of sodium carboxymethylcellulose.
Example 7
This example differs from example 1 only in that 97g of hard carbon precursor material and 3g of sodium carboxymethylcellulose are added.
Example 8
The difference between this example and example 1 is only that the hard carbon composite material in S3 is prepared by the following steps: and (3) directly mixing the hard carbon precursor/foam nickel material with 10g of sodium hexafluorophosphate, performing ball milling dispersion, carbonizing for 3 hours at 1500 ℃, and crushing to obtain the hard carbon composite material.
Example 9
This example differs from example 6 only in that 30g of sodium carboxymethylcellulose is replaced by 30g of sodium lignin sulfonate.
Comparative example 1
This comparative example differs from example 1 only in that 10g of sodium carboxymethylcellulose was replaced by 10g of bitumen binder.
SEM test
The hard carbon composite material prepared in example 1 was subjected to SEM test, and the result is shown in fig. 1;
As can be seen from FIG. 1, the hard carbon composite material has a granular structure and a slight bonding structure, and the grain size is 3-8 μm.
Physical and chemical property test
According to the testing method in the standard GB/T-24533-2019 lithium ion battery graphite anode material, the specific surface areas of the hard carbon composite materials prepared in the embodiment 1, the embodiment 4-5 and the embodiment 8 are tested, and the powder conductivity is tested by a four-probe tester; testing the OI value of the powder by an X-ray powder diffractometer; and the diffusion coefficient of the anode material was measured by GITT, and the measurement results are shown in table 2.
TABLE 2 physicochemical Property test results
The data of comparative examples 1, 4-5 and 8 show that the hard carbon composite materials prepared in examples 1 and 4-5 have better conductivity, OI value and diffusion coefficient compared with example 8, which indicates that the densification of the materials and the conductivity can be improved by depositing sodium salt by electrochemical deposition.
Button cell testing
Respectively taking the hard carbon composite materials prepared in the examples 1, 4-9 and the comparative example 1 as negative electrodes, and assembling the negative electrodes, a sodium sheet, an electrolyte and a diaphragm into a button cell in a glove box with argon and water contents lower than 0.1 ppm; wherein the diaphragm is celegard 2400; the electrolyte is a solution of NaPF6, the concentration of NaPF6 in the electrolyte is 1.1mol/L, and the solvent is a mixed solution obtained by mixing Ethylene Carbonate (EC) and diethyl carbonate (DMC) according to a weight ratio (1:1); the performance of the button cell is tested by adopting a blue-ray tester, and the test conditions are as follows: the charge and discharge rate of 0.1C was 0.005-2V, the cycle was stopped after 3 weeks, and the power-down rate performance (1C/0.1C) was measured, and the measurement results are shown in Table 3.
TABLE 3 results of button cell performance test
The data of comparative examples 1, 4-9 and 1 show that the hard carbon composite materials prepared in examples 1 and 4-5 have higher first efficiency and rate capability when used as the negative electrode, compared with examples 6-8 and 1; compared with example 9, when the hard carbon composite material prepared in example 6 is used as a negative electrode, the button cell has better first-time efficiency and rate capability; the method has the advantages that the sodium carboxymethyl cellulose is introduced into the hard carbon precursor/foam nickel material, and the first efficiency and the rate capability of the hard carbon composite material when the hard carbon composite material is used for the negative electrode of the button cell can be remarkably improved by regulating and controlling the mass ratio of the hard carbon precursor to the sodium hydroxymethyl cellulose.
Soft package battery performance test
The hard carbon composite materials prepared in example 1, examples 4 to 9 and comparative example 1 were respectively used as negative electrode active materials, and layered oxides (NaFe 1/3Mn1/3Ni1/3O 2) were used as positive electrode materials, electrolyte and separator to assemble a soft-pack battery of 5 Ah; wherein the diaphragm is celegard 2400, the electrolyte is NaPF6 solution (solvent is a mixed solution of EC and DEC with volume ratio of 1:1, and the concentration of NaPF6 is 1.3 mol/L); the cycle and rate performance of the prepared soft package battery were tested according to the following conditions:
cycle performance: testing the cycle performance of the battery at the temperature of 25+/-3 ℃ with the charge-discharge multiplying power of 1C/1C and the voltage range of 1.5-4.0V;
Quick charge performance: charging the battery to 100% SOC by adopting a constant current and constant voltage mode at a multiplying power of 1C, and then calculating a constant current ratio=constant current capacity/(constant current capacity+constant voltage capacity);
The test results are shown in table 4:
Table 4 results of soft pack battery performance test
The data of comparative examples 1, 4-9 and 1 show that the hard carbon composite materials prepared in examples 1 and 4-5 have better cycle performance and quick charge performance when used as the negative electrode of the soft-pack battery compared with examples 6-8 and 1; compared with example 9, when the hard carbon composite material prepared in example 6 is used as the negative electrode of the soft package battery, the cycle performance and the quick charge performance of the battery are higher; the method has the advantages that the hard carbon composite material adopts hard carbon, sodium doped amorphous carbon and foam nickel to form the inner core, and inorganic sodium salt to form the outer shell of the hard carbon material, and the mass ratio of the hard carbon precursor to the hydroxymethyl cellulose sodium is changed, so that the cycle performance and the quick charge performance of the hard carbon composite material when the hard carbon composite material is used for the negative electrode of the soft package battery can be remarkably 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 (10)
1. An electrochemical deposition method for preparing a hard carbon composite material is characterized in that the hard carbon composite material consists of an inner core and an outer shell; the inner core consists of hard carbon, sodium-doped amorphous carbon and foam nickel, and the outer shell is inorganic sodium salt;
the preparation method for preparing the hard carbon composite material by the electrochemical deposition method comprises the following steps:
s1, preparing a hard carbon precursor material: performing ball milling mixing on phenolic resin after first carbonization and diethyl ether, curing, crushing and performing second carbonization to obtain a hard carbon precursor material;
S2, preparing a hard carbon precursor/foam nickel material: mixing the hard carbon precursor material and sodium carboxymethylcellulose, and pressing the mixture on foam nickel to obtain a hard carbon precursor/foam nickel material;
s3, preparing a hard carbon composite material: and (3) taking the hard carbon precursor/foam nickel material as a working electrode, taking an ether compound containing inorganic sodium salt as a solvent, taking a saturated calomel electrode as a counter electrode, performing electrochemical deposition, washing, drying, and carbonizing for the third time to obtain the hard carbon composite material.
2. The method for preparing a hard carbon composite material by electrochemical deposition according to claim 1, wherein the inorganic sodium salt is one of sodium hexafluorophosphate, sodium trifluoromethane sulfonate, sodium tetrachloroborate, sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroantimonate, sodium benzoate, sodium p-toluenesulfonate, sodium difluorosulfimide, sodium tetrachloroaluminate, sodium tetrachloroferrite and sodium tetraphenylboron.
3. The method for preparing a hard carbon composite material by using an electrochemical deposition method according to any one of claims 1 to 2, comprising the following steps:
s1, preparing a hard carbon precursor material: performing ball milling mixing on phenolic resin after first carbonization and diethyl ether, curing, crushing and performing second carbonization to obtain a hard carbon precursor material;
S2, preparing a hard carbon precursor/foam nickel material: mixing the hard carbon precursor material and sodium carboxymethylcellulose, and pressing the mixture on foam nickel to obtain a hard carbon precursor/foam nickel material;
s3, preparing a hard carbon composite material: and (3) taking the hard carbon precursor/foam nickel material as a working electrode, taking an ether compound containing inorganic sodium salt as a solvent, taking a saturated calomel electrode as a counter electrode, performing electrochemical deposition, washing, drying, and carbonizing for the third time to obtain the hard carbon composite material.
4. The method for preparing the hard carbon composite material by using the electrochemical deposition method according to claim 3, wherein the mass ratio of the phenolic resin to the diethyl ether in the S1 is 100:100-500.
5. The method for preparing a hard carbon composite material by using an electrochemical deposition method according to claim 3, wherein the mass ratio of the hard carbon precursor material to the sodium carboxymethyl cellulose in the step S2 is 80:20-95:5.
6. The method for preparing a hard carbon composite material by using an electrochemical deposition method according to claim 3, wherein the molar concentration of the ether compound containing the inorganic sodium salt in the S3 is 0.5-1.5 mol/L.
7. The method for preparing a hard carbon composite material by an electrochemical deposition method according to claim 3, wherein the first carbonization temperature in the step S1 is 800-1500 ℃ and the carbonization time is 1-6 h; the temperature during curing is 250-500 ℃, and the curing time is 1-6 hours; the temperature of the secondary carbonization is 800-1500 ℃, the carbonization time is 1-6 h, and the carbonization is performed under the protection of argon inert gas.
8. The method for preparing a hard carbon composite material by using an electrochemical deposition method according to claim 3, wherein the temperature in the third carbonization in the step S3 is 500-800 ℃, and the carbonization time is 1-6 hours.
9. The method for preparing a hard carbon composite material by using an electrochemical deposition method according to claim 3, wherein the ether compound in S3 is one of diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
10. The method for preparing a hard carbon composite material by using an electrochemical deposition method according to claim 3, wherein the electrochemical deposition in the step S3 adopts a cyclic voltammetry, the scanning speed is 0.5-5 v/S, the voltage range is-2 v, and the scanning cycle number is 10-100 weeks.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311547998.2A CN117542977B (en) | 2023-11-20 | 2023-11-20 | Hard carbon composite material prepared by electrochemical deposition method and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311547998.2A CN117542977B (en) | 2023-11-20 | 2023-11-20 | Hard carbon composite material prepared by electrochemical deposition method and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117542977A CN117542977A (en) | 2024-02-09 |
| CN117542977B true CN117542977B (en) | 2024-05-17 |
Family
ID=89795307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311547998.2A Active CN117542977B (en) | 2023-11-20 | 2023-11-20 | Hard carbon composite material prepared by electrochemical deposition method and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117542977B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810922A (en) * | 2016-06-06 | 2016-07-27 | 中南大学 | Composite cathode material for lithium ion/sodium ion batteries and preparation method of composite anode material |
| CN110048107A (en) * | 2019-04-24 | 2019-07-23 | 陕西科技大学 | A kind of preparation method of self-supporting N doping hard carbon cathode material |
| CN115663157A (en) * | 2022-11-16 | 2023-01-31 | 晖阳(贵州)新能源材料有限公司 | Hard carbon composite material for lithium ion battery and preparation method thereof |
| CN116613292A (en) * | 2023-06-02 | 2023-08-18 | 深圳市拓邦锂电池有限公司 | Negative electrode material and preparation method thereof, negative electrode and preparation method thereof, and sodium ion battery |
| CN116646488A (en) * | 2023-06-05 | 2023-08-25 | 深圳钠博恩新材料有限公司 | Pre-lithiated hard carbon composite material, preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022117834A (en) * | 2021-02-01 | 2022-08-12 | 本田技研工業株式会社 | Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery provided with the same |
-
2023
- 2023-11-20 CN CN202311547998.2A patent/CN117542977B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810922A (en) * | 2016-06-06 | 2016-07-27 | 中南大学 | Composite cathode material for lithium ion/sodium ion batteries and preparation method of composite anode material |
| CN110048107A (en) * | 2019-04-24 | 2019-07-23 | 陕西科技大学 | A kind of preparation method of self-supporting N doping hard carbon cathode material |
| CN115663157A (en) * | 2022-11-16 | 2023-01-31 | 晖阳(贵州)新能源材料有限公司 | Hard carbon composite material for lithium ion battery and preparation method thereof |
| CN116613292A (en) * | 2023-06-02 | 2023-08-18 | 深圳市拓邦锂电池有限公司 | Negative electrode material and preparation method thereof, negative electrode and preparation method thereof, and sodium ion battery |
| CN116646488A (en) * | 2023-06-05 | 2023-08-25 | 深圳钠博恩新材料有限公司 | Pre-lithiated hard carbon composite material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117542977A (en) | 2024-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021042990A1 (en) | Positive electrode active material, preparation method therefor, positive electrode sheet, lithium ion secondary battery and related battery module, battery pack and device thereof | |
| EP3933981B1 (en) | Positive electrode active material and preparation method therefor, positive electrode plate, lithium ion secondary battery, and battery module, battery pack, and apparatus containing such lithium-ion secondary battery | |
| EP3968430B1 (en) | Secondary battery and apparatus containing the secondary battery | |
| US20240097124A1 (en) | Positive active material, positive electrode plate and lithium-ion secondary battery | |
| WO2021042983A1 (en) | Positive electrode active material and preparation method therefor, positive electrode plate, lithium-ion secondary battery and battery module comprising same, battery pack, and device | |
| WO2021042987A1 (en) | Positive electrode active material, preparation method therefor, positive electrode sheet, lithium ion secondary battery, and battery module, battery pack and device containing lithium ion secondary battery | |
| CN109686923B (en) | Preparation method of pre-lithium-intercalated negative electrode, pre-lithium-intercalated negative electrode prepared by preparation method, energy storage device, energy storage system and electric equipment | |
| CN109935891B (en) | Lithium cobaltate digital lithium ion battery with high and low temperature consideration | |
| WO2021042977A1 (en) | Positive electrode active material and preparation method therefor, positive electrode plate, lithium ion secondary battery and battery module comprising lithium ion secondary battery, battery pack, and apparatus | |
| WO2021043149A1 (en) | Positive electrode active material, preparation method therefor, positive electrode plate, lithium ion secondary battery and device comprising lithium ion secondary battery | |
| CN115663157B (en) | Hard carbon composite material for lithium ion battery and preparation method thereof | |
| CN111276692A (en) | Lithium ion battery negative electrode active material, preparation method thereof and lithium ion battery | |
| CN111969182A (en) | Positive pole piece, preparation method thereof, and lithium ion secondary battery, electric vehicle and electronic product related to positive pole piece | |
| CN109962231B (en) | Metal foil used as lanthanum ion secondary battery cathode, lanthanum ion secondary battery and preparation method thereof | |
| CN113224464A (en) | Lithium-sulfur battery taking CoS/NS co-doped graphene composite material coated diaphragm as intermediate layer | |
| CN114613974A (en) | Long-life quick-charging type lithium ion battery cathode material and preparation method thereof | |
| CN109713225A (en) | Lithium ion secondary battery | |
| CN113299897B (en) | Na (Na) 3 V 2 (PO 4 ) 3 Mixed ion full battery with @ C as positive electrode material | |
| CN116646488A (en) | Pre-lithiated hard carbon composite material, preparation method and application thereof | |
| CN115020688B (en) | High-performance silica anode material and preparation method and application thereof | |
| CN117542977B (en) | Hard carbon composite material prepared by electrochemical deposition method and preparation method thereof | |
| CN103367728A (en) | Activated natural graphite modified Li2FeSiO4 cathode material and its preparation method | |
| CN116130659A (en) | Hard carbon composite material, material preparation method, electrode plate and battery | |
| CN115663118A (en) | Positive electrode plate, secondary battery and power utilization device | |
| CN110980672B (en) | Lithium ion battery negative electrode active material, preparation method thereof and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |