CN116002659A - Hard carbon anode material, preparation method and application thereof, and battery - Google Patents
Hard carbon anode material, preparation method and application thereof, and battery Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 70
- 239000010405 anode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001509 sodium citrate Substances 0.000 claims abstract description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000005416 organic matter Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 229920002472 Starch Polymers 0.000 claims abstract description 5
- 229930006000 Sucrose Natural products 0.000 claims abstract description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 5
- 239000008107 starch Substances 0.000 claims abstract description 5
- 235000019698 starch Nutrition 0.000 claims abstract description 5
- 239000005720 sucrose Substances 0.000 claims abstract description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000001632 sodium acetate Substances 0.000 claims abstract description 4
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 4
- 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 abstract description 3
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000001527 calcium lactate Substances 0.000 claims abstract description 3
- 229960002401 calcium lactate Drugs 0.000 claims abstract description 3
- 235000011086 calcium lactate Nutrition 0.000 claims abstract description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 3
- 235000011083 sodium citrates Nutrition 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000007773 negative electrode material Substances 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 17
- 229910001415 sodium ion Inorganic materials 0.000 claims description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000009656 pre-carbonization Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000004154 testing of material 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
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- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a hard carbon anode material, a preparation method and application thereof, and a battery. The preparation method of the hard carbon anode material comprises the following steps: evaporating the solvent from the organic matters and the organic salt in the process of mixing reaction to prepare a precursor; pre-carbonizing the precursor to obtain a pre-carbonized product; carbonizing the pre-carbonized product to obtain carbide; acid washing is carried out on carbide to prepare a hard carbon anode material; wherein the organic matter comprises one or more of sucrose, starch, citric acid and urea, the organic salt comprises one or more of sodium acetate, calcium lactate, sodium citrate and sodium carboxymethylcellulose, and the solvent is a mixed solution of ethanol and water. The hard carbon anode material prepared by the invention has higher first coulomb efficiency and specific charge-discharge capacity.
Description
Technical Field
The invention relates to a hard carbon anode material, a preparation method and application thereof, and a battery.
Background
In recent years, with the gradual maturity of lithium ion battery technology, the production and sales of new energy automobiles are continuously increased, so that lithium resources are more scarce and the price of lithium sources is continuously increased. Due to the important advantages of abundant sodium resources and low cost, the research of sodium ion batteries gradually draws extensive attention of scientific researchers. In addition, the sodium ion battery has a similar working principle as a lithium ion battery, the energy density of the sodium ion battery is close to that of a power lithium iron phosphate battery, and the sodium ion battery has a lot of commonalities in research and production, and is easier for mass production. Therefore, the sodium ion battery has good application potential in the fields of new energy automobiles, large-scale energy storage and the like.
The negative electrode material is an important component of sodium ion batteries. To a great extent, the performance of the negative electrode material plays an important role in the overall performance of the sodium ion battery. Among a plurality of negative electrode materials (phosphorus-based, tin-based, bismuth-based and the like), the hard carbon negative electrode material has the advantages of abundant raw material sources, simple preparation process, stable electrochemical performance and the like, and is considered as a sodium ion negative electrode material which is mainstream in the future. However, the first coulombic efficiency and the specific charge-discharge capacity of the hard carbon cathode material developed in the current stage are low, and the development of sodium ion batteries is severely restricted.
Disclosure of Invention
The invention aims to overcome the defects of low first coulombic efficiency and low specific charge-discharge capacity of a hard carbon negative electrode material in the prior art, and provides the hard carbon negative electrode material, a preparation method and application thereof, and a battery. The hard carbon negative electrode material has high first coulombic efficiency and specific charge-discharge capacity.
The invention solves the technical problems by the following technical scheme:
the invention provides a preparation method of a hard carbon anode material, which comprises the following steps:
s1: evaporating the solvent from the organic matters and the organic salt in the process of mixing reaction to prepare a precursor;
s2: pre-carbonizing the precursor to obtain a pre-carbonized product;
s3: carbonizing the pre-carbonized product to obtain carbide;
s4: acid washing is carried out on the carbide to prepare the hard carbon anode material;
in step S1, the organic matter includes one or more of sucrose, starch, citric acid and urea, the organic salt includes one or more of sodium acetate, calcium lactate, sodium citrate and sodium carboxymethylcellulose, and the solvent is a mixed solution of ethanol and water.
In step S1, preferably, the organic substance is urea.
In step S1, preferably, the organic salt is sodium citrate.
In step S1, the mass of the organic matter and the organic salt is preferably 1:50-20:1, more preferably 2:1-8:1, for example 2:1, 4:1 or 8:1.
In step S1, the volume ratio of ethanol to water is preferably 1:30-10:1, more preferably 1:1-3:1, for example 1:1, 2:1 or 3:1.
In step S1, the mixing reaction is preferably carried out for a period of time ranging from 0.5 to 24 hours, for example 2 hours.
In step S1, the temperature of the mixing reaction is preferably 30 to 150 ℃, for example 100 ℃,120 ℃ or 150 ℃.
The time and temperature of the mixing reaction will generally be the time and temperature of agitation, as will be appreciated by those skilled in the art.
In step S2, the pre-carbonization treatment is preferably performed under a protective atmosphere.
In step S3, the carbonization treatment is preferably performed under a protective atmosphere.
In step S2 and step S3, the protective atmosphere is preferably argon, nitrogen or 5%H 2 Ar mixture, such as nitrogen.
In step S3, the gas flow rate during the carbonization treatment is preferably 0.01-10L/min, for example 0.5L/min.
In step S2, the temperature of the pre-carbonization treatment is preferably 300-1000 ℃, for example 600 ℃.
In step S2, the pre-carbonization treatment is preferably performed for a period of 0.5 to 12 hours, for example, 2 hours.
In step S3, the temperature is preferably raised to the carbonization treatment temperature at a rate of 0.1-20deg.C/min, for example, 5deg.C/min.
In step S3, the carbonization treatment is preferably performed at a temperature of 1000 to 2000 ℃, for example 1100 ℃, 1300 ℃, or 1500 ℃.
In step S3, the carbonization treatment is preferably performed for 0.5 to 36 hours, for example, 4 hours.
In step S4, preferably, the acid includes one or more of sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid, such as hydrochloric acid.
In step S4, the concentration of the acid is preferably 0.01 to 20mol/L, for example 1mol/L.
In step S4, preferably, the pickling further includes stirring, filtering, and drying steps.
Preferably, the stirring time is 0.1 to 36 hours, for example 12 hours.
Preferably, the temperature of the drying is 50-180 ℃, for example 120 ℃.
In the present invention, the inventors found that the groups of the organic substance and the groups in the organic salt undergo a crosslinking reaction to produce a pre-carbonized product, and at the same time, the organic salt in the pre-carbonized product is uniformly dispersed in the pre-carbonized product. In the high-temperature carbonization process, more disordered graphite microcrystals and more micropores are generated, and the high-performance hard carbon anode material is prepared.
The invention provides a hard carbon negative electrode material prepared by the preparation method of the hard carbon negative electrode material.
In the present invention, the hard carbon negative electrode material preferably has a particle diameter of 8.9 to 10.1 μm, for example, 8.9 μm, 9.2 μm, 9.4 μm, 9.5 μm, 9.6 μm, 9.7 μm, 9.8 μm or 10.1 μm.
In the invention, the tap density of the hard carbon anode material is preferably 0.78-0.85g/cm 3 For example 0.78g/cm 3 、0.79g/cm 3 、0.80g/cm 3 、0.81g/cm 3 、0.82g/cm 3 、0.83g/cm 3 、0.84g/cm 3 Or 0.85g/cm 3 。
In the invention, the specific surface area of the hard carbon anode material is preferably 1.6-3.7m 2 /g, e.g. 1.6m 2 /g、1.7m 2 /g、1.9m 2 /g、2.0m 2 /g、2.1m 2 /g、2.2m 2 /g、2.3m 2 /g、2.4m 2 /g、2.8m 2 /g、3.0m 2 /g or 3.7m 2 /g。
In the present invention, the pore diameter of the micropores of the hard carbon negative electrode material is preferably 0.40 to 0.90nm, for example, 0.40nm, 0.42nm, 0.45nm, 0.47nm, 0.49nm, 0.50nm, 0.52nm, 0.53nm, 0.55nm, 0.65nm, 0.66nm, 0.75nm, 0.85nm, 0.88nm or 0.90nm.
The invention also provides application of the hard carbon anode material in a battery.
In the present invention, the battery is preferably a sodium ion battery.
The invention also provides a battery, which comprises the hard carbon anode material.
In the present invention, the battery is preferably a sodium ion battery.
The invention has the positive progress effects that:
(1) The invention synthesizes the hard carbon anode material by adopting specific organic matters and organic salts, improves the disorder degree of the carbonization process of the material and improves the micropore structure. The hard carbon negative electrode material prepared by the method has rich surface defects and large graphite microcrystalline interlayer spacing, provides more reactive sites, enhances ion diffusion kinetics, improves the utilization rate of sodium ions, and improves the first coulomb efficiency and the specific charge-discharge capacity of the hard carbon negative electrode material.
(2) The proper micropores in the hard carbon negative electrode material prepared by the method can prevent the infiltration of electrolyte, reduce the generation of a solid electrolyte membrane on the surface of the hard carbon, and can obtain higher first coulomb efficiency.
(3) The three-dimensional multi-stage structure of the hard carbon anode material prepared by the invention can provide more electron conduction channels, enhance electron transmission and improve overall conductivity.
(4) The invention has simple process, good repeatability, low production cost and low energy consumption, is very suitable for industrial production, and has wide application prospect on sodium ion batteries.
Drawings
FIG. 1 is a field emission scanning electron microscope (FEMS) of the hard carbon negative electrode material prepared in example 1.
FIG. 2 is an X-ray diffraction chart of the hard carbon negative electrode material prepared in example 1.
Fig. 3 is a graph showing the first charge and discharge at a current density of 0.1C for the hard carbon anode material prepared in example 1.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention.
Example 1
Preparing a hard carbon precursor: 100g of urea and 25g of sodium citrate were weighed and dissolved in a mixed solution of 250mL of absolute ethanol and 250mL of deionized water, and stirred for 2 hours to allow them to be sufficiently dissolved. Then, the temperature of the solvent was evaporated by heating while stirring was set to 100 ℃. Finally, the dried white powder is obtained as the precursor.
Preparation of a pre-carbonized product: 50g of the precursor is put into a porcelain square boat, air is purged by nitrogen, and the nitrogen flow speed is regulated to be 0.5L/min. Then, the temperature was raised to 600℃at a heating rate of 3℃per minute, and heat treatment was carried out for 2 hours, to obtain a black pre-carbonized product.
Preparation of carbide: 40g of the pre-carbonized product is put into a porcelain square boat, air is firstly purged by nitrogen, and the nitrogen flow speed is regulated to be 0.5L/min. Then, the temperature was raised to 1300℃at a heating rate of 3℃per minute, and heat treatment was carried out for 4 hours, to obtain a black powder sample.
And (3) pickling the carbonized material by using 1mol/L hydrochloric acid, stirring for 12 hours, filtering, and vacuum drying at 120 ℃ to obtain the hard carbon anode material.
Example 2
The procedure of example 1 was followed, except that the amount of urea was 50g.
Example 3
The procedure of example 1 was followed except that the amount of sodium citrate was 12.5g.
Example 4
The procedure of example 1 was followed except that the organic material was sucrose.
Example 5
The procedure of example 1 was followed except that the organic material was starch.
Example 6
The procedure of example 1 was followed, except that the volume ratio of ethanol to water was 2:1.
example 7
The procedure of example 1 is followed, except that the volume ratio of ethanol to water is 3:1.
example 8
The procedure of example 1 was followed, except that the temperature of the evaporating solvent was 150 ℃.
Example 9
The procedure of example 1 was followed, except that the temperature of the evaporated solvent was 120 ℃.
Example 10
The procedure of example 1 was followed except that the organic salt was sodium acetate.
Example 11
The procedure of example 1 was followed except that the inert atmosphere for carbonization was high purity argon.
Example 12
The procedure of example 1 is followed, except that the inert atmosphere for carbonization is 5% H 2 Ar mixture.
Example 13
The procedure of example 1 was followed, except that the high-temperature carbonization treatment temperature was 1500℃and the time was 4 hours.
Example 14
The procedure of example 1 was followed, except that the high-temperature carbonization treatment was carried out at 1100℃for 4 hours.
Comparative example 1
The procedure of example 1 was followed, except that urea was not added.
Comparative example 2
The procedure of example 1 was followed except that sodium citrate was not added.
Comparative example 3
The procedure of example 1 was followed except that only water was added to the solvent.
Comparative example 4
The procedure of example 1 was followed except that only ethanol was added to the solvent.
Effect example 1 testing of material properties of hard carbon negative electrode material
Test object: examples 1 to 14 and comparative examples 1 to 4.
Test equipment: particle size tester, full-automatic specific surface tester, tap density meter and blue electric testing system
Test results: as shown in table 1 below and in fig. 1-2.
As shown in fig. 1, the material of example 1 has a size of about 10 μm and a three-dimensional multi-stage structure.
As shown in fig. 2, the hard carbon anode material of example 1 has distinct swelling peaks at 2θ=24.8° and 43.7 °, corresponding to (002) and (100) crystal planes of the carbon material, respectively. XRD pattern test results show that the hard carbon anode material is amorphous carbon with poor crystallinity.
TABLE 1 Material Performance test results
As is clear from Table 1, the hard carbon negative electrode materials in examples 1 to 14 had particle diameters of 8.9 to 10.1. Mu.m, and were compactedThe degree of the mixture is 0.78-0.85g/cm 3 The specific surface area is 1.6-3.7m 2 And/g, wherein the pore diameter of the micropores is 0.40-0.90nm; the specific surface areas of examples 1-14 were all smaller than comparative examples 1-4.
Effect example 2 electrical performance test
Test object: examples 1 to 14 and comparative examples 1 to 4.
The specific assembly method of the battery is as follows:
the electrochemical lithium storage performance of the materials was tested using CR2016 type button cells. 90% of electrode active material, 5% of acetylene black and 5% of carboxymethyl cellulose (CMC) binder (0.05 g/mL aqueous solution) are weighed according to the mass ratio, and placed in a small beaker to be mixed and stirred for 8 hours, so as to obtain the electrode slurry which is uniformly mixed. Uniformly coating the slurry on copper foil, drying in a hollow oven at 60-80 ℃, tabletting and punching the dried pole piece to prepare a wafer with the diameter of 12mm, and weighing the electrode piece by adopting a precision balance after vacuum drying for 6 hours at 80 ℃. And (5) weighing the blank copper foil at the same position after slicing, wherein the mass of the active substance on each electrode plate is 70% of the difference value. Immediately transferring the dried and weighed electrode sheet into a glove box (Super 1220/750, milklena (China) Inc., oxygen gas) filled with an argon gas protective atmosphere<5ppm of water<1 ppm) was assembled with a battery, a metallic sodium sheet as a counter electrode, 1mol/L NaPF 4 Ethylene glycol dimethyl ether (DME) is used as electrolyte, whatman GF/A is used as diaphragm, and foaming nickel sheet is used as filler to prepare CR2016 type button cell.
The testing method comprises the following steps:
and (3) charge and discharge testing: and (3) performing charge and discharge tests on the LAND battery test system, wherein the LAND battery test system is set in a constant-current charge and discharge mode, the adopted current density is set as a set value, and the charge and discharge voltage range is set to be 0.01-2V.
Test results: as shown in table 2 and fig. 3.
As shown in fig. 3, the specific capacities of the hard carbon anode material assembled battery of example 1 for the first charge and discharge were 400.6mAh/g and 446.2mAh/g, respectively, corresponding to a first coulombic efficiency (ICE) as high as 89.8%.
TABLE 2 electrochemical Performance measurement results
As can be seen from Table 2, the first coulombic efficiencies of examples 1 to 14 were not less than 83.2%, which are all greater than those of comparative examples 1 to 4. The first charge specific capacity of examples 1-14 was equal to or greater than 332.6mAh/g, the first discharge specific capacity was equal to or greater than 391.9mAh/g, both of which were greater than the first charge/discharge specific capacity of comparative examples, and the reversible specific capacities of examples 2, 3, 13 and 14 were equal to or greater than 330.0mAh/g, both of which were higher than the reversible specific capacities of comparative examples 1-4.
The hard carbon anode material assembled batteries prepared in examples 1, 2 and 3 were superior to comparative examples 1 and 2 in both initial coulombic efficiency and specific charge/discharge capacity. Therefore, the electrochemical performance of the battery assembled by the hard carbon anode material prepared by mutually matching specific organic matters and organic salts is better.
Compared with comparative examples 3 and 4, the first coulombic efficiency and the first charge-discharge specific capacity of the battery prepared by the hard carbon anode material prepared by the mixed solution of deionized water and ethanol as the solvent are improved, which shows that the electrochemical performance of the battery assembled by the hard carbon anode material prepared by the mixed solution of deionized water and ethanol is better.
As can be seen from the first coulombic efficiency and the specific charge/discharge capacity of the batteries assembled from the hard carbon negative electrode materials prepared in examples 1, 2 and 3, as the mass ratio of the organic matter to the organic salt increases, the first coulombic efficiency and the specific charge/discharge capacity show a tendency of increasing first and then decreasing, and the mass ratio of the organic matter to the organic salt is 4: and 1, the prepared hard carbon cathode material assembled battery has the highest initial coulomb efficiency and initial charge/discharge specific capacity.
The first coulombic efficiency and specific charge/discharge capacity of the battery assembled from the hard carbon negative electrode materials prepared in examples 1, 4 and 5 were found to be highest when urea was selected as the organic material, but the first coulombic efficiency of the battery assembled from the hard carbon negative electrode material prepared when starch was selected as the organic material was inferior to those of urea and sucrose.
The first coulombic efficiency and the charge/discharge specific capacity of the batteries assembled from the hard carbon negative electrode materials prepared in examples 1, 6 and 7 show that the higher the volume ratio of ethanol to water, the lower the first coulombic efficiency, and the first charge/discharge specific capacity shows a tendency of decreasing and then increasing. When the volume ratio of ethanol to water is 1:1, the electrochemical performance is better.
The first coulombic efficiency and the charge/discharge specific capacity of the battery assembled from the hard carbon negative electrode materials prepared in examples 1, 8 and 9 show that the higher the temperature of the evaporating solvent, the first coulombic efficiency and the first charge/discharge specific capacity thereof show a tendency to decrease and then increase. When the temperature of the evaporating solvent is 100 ℃, the electrochemical performance of the battery assembled by the prepared hard carbon anode material is better.
The first coulombic efficiency and the specific charge/discharge capacity of the battery assembled from the hard carbon negative electrode materials prepared in examples 1 and 10 are shown to be better when sodium citrate is selected as the organic salt.
The first coulombic efficiency and the specific charge/discharge capacity of the battery assembled from the hard carbon negative electrode materials prepared in examples 1, 11 and 12 were found to be good when nitrogen was selected as the inert atmosphere.
As can be seen from the first coulombic efficiency and the charge/discharge specific capacity of the batteries assembled from the hard carbon negative electrode materials prepared in examples 1, 13 and 14, the first coulombic efficiency and the first charge/discharge specific capacity of the prepared hard carbon negative electrode materials tended to increase and then decrease with increasing carbonization treatment temperature.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the principles and spirit of the invention, but such changes and modifications fall within the scope of the invention.
Claims (10)
1. The preparation method of the hard carbon anode material is characterized by comprising the following steps:
s1: evaporating the solvent from the organic matters and the organic salt in the process of mixing reaction to prepare a precursor;
s2: pre-carbonizing the precursor to obtain a pre-carbonized product;
s3: carbonizing the pre-carbonized product to obtain carbide;
s4: acid washing is carried out on the carbide to prepare the hard carbon anode material;
in step S1, the organic matter includes one or more of sucrose, starch, citric acid and urea, the organic salt includes one or more of sodium acetate, calcium lactate, sodium citrate and sodium carboxymethylcellulose, and the solvent is a mixed solution of ethanol and water.
2. The method for producing a hard carbon negative electrode material according to claim 1, wherein in step S1, the organic substance is urea;
and/or, the organic salt is sodium citrate;
and/or the mass ratio of the organic matter to the organic salt is 1:50 to 20:1, preferably 2:1 to 8:1, for example 2:1, 4:1 or 8:1;
and/or the ethanol to water volume ratio is from 1:30 to 10:1, preferably from 1:1 to 3:1, for example 1:1, 2:1 or 3:1.
3. The method for producing a hard carbon negative electrode material according to claim 1, wherein in step S1, the time of the mixing reaction is 0.5 to 24 hours, for example, 2 hours;
and/or the temperature of the mixing reaction is 30-150 ℃, e.g. 100 ℃,120 ℃ or 150 ℃.
4. The method for producing a hard carbon negative electrode material according to claim 1, wherein in step S2, the pre-carbonization treatment is performed under a protective atmosphere of argon, nitrogen or 5%H 2 Ar mixed gas;
and/or the temperature of the pre-carbonization treatment is 300-1000 ℃, such as 600 ℃;
and/or the pre-carbonization treatment is for a time of 0.5-12 hours, for example 2 hours.
5. The method for producing a hard carbon negative electrode material according to claim 1, wherein in step S3, the carbonization treatment is performed under a protective atmosphere of argon, nitrogen or 5%H 2 Ar mixed gas;
and/or, during the carbonization treatment, a gas flow rate of 0.01 to 10L/min, for example 0.5L/min;
and/or, the rate of heating to the carbonization treatment temperature is 0.1-20 ℃/min, such as 5 ℃/min;
and/or the carbonization treatment is at a temperature of 1000-2000 ℃, such as 1100 ℃, 1300 ℃, or 1500 ℃;
and/or the carbonization treatment is for a time of 0.5 to 36 hours, for example 4 hours.
6. The method for producing a hard carbon negative electrode material according to claim 1, wherein in step S4, the acid includes one or more of sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid, such as hydrochloric acid;
and/or the concentration of the acid is 0.01 to 20mol/L, for example 1mol/L;
and/or, the pickling step further comprises stirring, filtering and drying;
wherein the time of stirring is preferably 0.1 to 36 hours, for example 12 hours;
the temperature of the drying is preferably 50-180 ℃, for example 120 ℃.
7. A hard carbon negative electrode material produced by the production method of a hard carbon negative electrode material according to any one of claims 1 to 6.
8. The hard carbon anode material according to claim 7, wherein the hard carbon anode material has a particle size of 8.9-10.1 μm, such as 8.9 μm, 9.2 μm, 9.4 μm, 9.5 μm, 9.6 μm, 9.7 μm, 9.8 μm or 10.1 μm;
and/or the tap density of the hard carbon anode material is 0.78-0.85g/cm 3 For example 0.78g/cm 3 、0.79g/cm 3 、0.80g/cm 3 、0.81g/cm 3 、0.82g/cm 3 、0.83g/cm 3 、0.84g/cm 3 Or 0.85g/cm 3 ；
And/or the specific surface area of the hard carbon anode material is 1.6-3.7m 2 /g, e.g. 1.6m 2 /g、1.7m 2 /g、1.9m 2 /g、2.0m 2 /g、2.1m 2 /g、2.2m 2 /g、2.3m 2 /g、2.4m 2 /g、2.8m 2 /g、3.0m 2 /g or 3.7m 2 /g；
And/or the hard carbon anode material has a micropore size of 0.40-0.90nm, such as 0.40nm, 0.42nm, 0.45nm, 0.47nm, 0.49nm, 0.50nm, 0.52nm, 0.53nm, 0.55nm, 0.65nm, 0.66nm, 0.75nm, 0.85nm, 0.88nm, or 0.90nm.
9. Use of a hard carbon negative electrode material according to claim 7 or 8 in a battery, preferably a sodium ion battery.
10. A battery, preferably a sodium ion battery, characterized in that it comprises a hard carbon negative electrode material according to claim 7 or 8.
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