CN115360348A - Novel hard carbon material and preparation method and application thereof - Google Patents
Novel hard carbon material and preparation method and application thereof Download PDFInfo
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- CN115360348A CN115360348A CN202210880395.3A CN202210880395A CN115360348A CN 115360348 A CN115360348 A CN 115360348A CN 202210880395 A CN202210880395 A CN 202210880395A CN 115360348 A CN115360348 A CN 115360348A
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- hard carbon
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 118
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 238000003763 carbonization Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 102000020897 Formins Human genes 0.000 claims description 16
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- 238000001035 drying Methods 0.000 claims description 16
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- 238000004146 energy storage Methods 0.000 claims description 9
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- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
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- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 claims description 2
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- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 229930182830 galactose Natural products 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose 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[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 claims description 2
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000010356 sorbitol Nutrition 0.000 claims description 2
- UQZIYBXSHAGNOE-XNSRJBNMSA-N stachyose 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[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO[C@@H]3[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O3)O)O2)O)O1 UQZIYBXSHAGNOE-XNSRJBNMSA-N 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000012360 testing method Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 24
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- 239000003792 electrolyte Substances 0.000 description 13
- 229910001415 sodium ion Inorganic materials 0.000 description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 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 8
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- 229910052708 sodium Inorganic materials 0.000 description 8
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
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- 238000009792 diffusion process Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
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- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 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 description 1
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- 239000007833 carbon precursor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 229910001414 potassium ion Inorganic materials 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
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
- H01M4/58—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a novel hard carbon material and a preparation method and application thereof. The preparation method of the hard carbon material comprises the following steps: (1) Dissolving carbohydrate in an acid solution, quickly heating to evaporate the solvent, and dehydrating or partially dehydrating the carbohydrate to obtain a pre-carbonized precursor; (2) And (2) carbonizing the precursor prepared in the step (1) at high temperature in an inert atmosphere to obtain the hard carbon material. The hard carbon material prepared by the method has higher specific capacity and first-turn coulombic efficiency as a negative electrode material, and has quick charge-discharge capacity and excellent cycle stability.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a novel hard carbon material and a preparation method and application thereof.
Background
With the increasing requirements of emerging technical fields such as electric vehicles, robots, unmanned aerial vehicles, large-scale energy storage and the like on the aspects of energy density and power density of secondary batteries, it becomes especially important to simultaneously improve the energy density and power density of current Lithium Ion Batteries (LIBs) and Sodium Ion Batteries (SIBs) by researching and developing novel cathode materials. The interlayer spacing of the graphite cathode is low, the multiplying power performance is poor, and the continuous improvement of the current LIB power density is seriously influenced. The hard carbon material with relatively large carbon layer spacing has the capability of quickly de-embedding lithium ions, and is the first choice of the high-power-density type LIB cathode material. In addition, the hard carbon material can realize reversible deintercalation of sodium ions due to the larger carbon layer spacing, has high specific capacity, and is the best choice for the current SIB battery cathode material. Therefore, the development of a hard carbon anode material with low cost and high performance is crucial for both LIB and SIB batteries. However, achieving a unification of high mass/volume specific capacity and high rate capability of hard carbon materials remains a significant challenge.
The improvement of the rate capability of the carbon cathode material is mainly influenced by the diffusion kinetics of ions and electrons. For the ion diffusion process, the nano structure, the porous structure or the hollow structure can shorten the ion diffusion distance, and the increased carbon layer distance can reduce the ion diffusion resistance. The above structures can effectively promote ion diffusion kinetics. However, all of the above methods inevitably result in high specific surface area and low packing density, ultimately resulting in low Initial Coulombic Efficiency (ICE) and non-ideal volumetric specific capacity. For improving electron diffusion kinetics, sp 2 The hybridized carbon layer can efficiently conduct electrons, and the electron conduction can be improved to a certain extent by the additional conductive carbon and the like. Therefore, ion and electron diffusion dynamics are comprehensively considered, the carbon layer spacing of the hard carbon material is properly increased, the nano porous structure which can be accessed by electrolyte is reduced, the specific surface area is reduced, and the method is an effective way for realizing high mass/volume specific capacity and high rate performance unification of the hard carbon material. However, at present, the preparation of hard carbon materials with low cost, few nano-porous structures and controllable carbon layer spacing in a certain range is still difficult.
Disclosure of Invention
In order to improve the technical problems, the invention aims to provide a high-performance hard carbon material and a preparation method and application thereof.
The invention provides the following technical scheme:
a method of preparing a hard carbon material, comprising the steps of:
(1) Dissolving carbohydrate in an acid solution, quickly heating to evaporate the solvent, and dehydrating or partially dehydrating the carbohydrate to obtain a pre-carbonized precursor;
(2) And (2) carbonizing the precursor prepared in the step (1) at high temperature in an inert atmosphere to obtain the hard carbon material.
According to an embodiment of the invention, in step (1), the carbohydrate is soluble, for example at least one selected from the group consisting of glucose, fructose, sucrose, galactose, lactose, maltose, soluble hemicellulose, pectin, trehalose, raffinose, stachyose, sorbitol, mannitol, xylitol, gluconic acid and water-soluble starch, for example one, two or more.
According to an embodiment of the present invention, in the step (1), the acid solution has a dehydration property, for example, one or a mixed solution of two or more selected from sulfuric acid, phosphoric acid, polyphosphoric acid, and selenic acid.
According to an embodiment of the present invention, in the step (1), the concentration of the acid solution is 0.001 to 0.5mol L -1 Preferably 0.01 to 0.2mol L -1 For example, 0.01mol L -1 、0.02mol L -1 、0.04mol L -1 、0.08mol L -1 、0.1mol L -1 、0.2mol L -1 。
According to the embodiment of the invention, the rapid temperature rise means that the temperature rise rate is 5-50 ℃ for min -1 Heating to the drying temperature and then preserving the heat for a period of time.
Preferably, the drying temperature is 100 to 250 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ and 250 ℃.
Preferably, the incubation time is 2 to 24 hours, for example 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours.
Illustratively, the drying temperature is 120-200 ℃ and the holding time is 2-12 h, such as 2h, 4h, 6h, 8h, 10h, 12h.
According to an embodiment of the present invention, in the step (2), the high temperature carbonization temperature is 600 to 2000 ℃, for example, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1200 ℃, 1400 ℃, 1600 ℃, 1800 ℃, 2000 ℃; the heat preservation time at the high-temperature carbonization temperature is 0.5-20 h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h and 20h.
Illustratively, the temperature of the high-temperature carbonization is 800-1500 ℃, and the holding time is 1-10 h, such as 2h, 4h, 6h, 8h, 10h.
According to an embodiment of the present invention, the high temperature carbonization includes a temperature raising stage and a heat preservation treatment, and preferably, the heat preservation treatment is performed after the temperature is raised to the temperature of the high temperature carbonization.
According to an embodiment of the present invention, the temperature raising stage is to raise the temperature to the temperature of the high-temperature carbonization at a certain temperature raising rate.
Preferably, the heating rate is 0.1-20 ℃ min -1 Preferably 0.5 to 10 ℃ for min -1 E.g. 1 ℃ min -1 、5℃min -1 。
According to an embodiment of the invention, the preparation method further comprises: (3) Pulverizing the hard carbon material prepared in the step (2) to a suitable particle size.
According to an embodiment of the invention, the hard carbon material has a particle size of 0.1 to 50 μm, preferably 1 to 30 μm, e.g. 22, 14, 25, 12 μm.
The invention also provides a hard carbon material which comprises a quasi graphite structure and a pore structure consisting of disordered carbon.
According to an embodiment of the present invention, the quasi-graphitic structure is a layer in which the (002) interplanar spacing is 0.35 to 0.7nm; preferably 0.35 to 0.5nm, for example 0.5nm.
According to an embodiment of the present invention, the size of the pore structure composed of the disordered carbon is 0.35 to 0.7nm; preferably 0.4 to 0.6nm, for example, 0.394nm, 0.391nm, 0.422nm, 0.397nm, 0.388nm, 0.384nm, 0.386nm, 0.396nm, 0.385nm.
According to an embodiment of the present invention, the hard carbon material is prepared by the above-described preparation method.
According to an embodiment of the present invention, the hard carbon material has a gram capacity of 200 to 650mAh g -1 For example, 250 to 600mAh g -1 、200～450mAh g -1 . Illustratively, when the hard carbon material is applied to a lithium ion battery, the gram capacity of the hard carbon material is 250-600 mAh g -1 . Illustratively, when the hard carbon material is applied to a sodium ion battery, the gram capacity of the hard carbon material is 200-450 mAh g -1 。
According to an embodiment of the invention, the hard carbon material has a particle size of 0.1 to 50 μm, preferably 1 to 30 μm, for example 22 μm, 14 μm, 25 μm, 12 μm, 10 μm, 13 μm.
According to an embodiment of the present invention, the hard carbon material has a specific surface area of 0.1 to 1000m 2 g -1 Preferably 0.1 to 200m 2 g -1 For example 17.3m 2 g -1 、21.4m 2 g -1 、253m 2 g -1 、32.3m 2 g -1 、5.7m 2 g -1 、156m 2 g -1 、132m 2 g -1 、20.2m 2 g -1 、18.4m 2 g -1 。
The invention also provides a negative electrode material which comprises the hard carbon material.
The invention also provides an electrode which comprises the hard carbon material and/or the negative electrode material.
According to an embodiment of the present invention, the electrode is prepared as follows: and preparing the hard carbon material and/or the negative electrode material, a binder and a conductive agent into mixed slurry according to a certain proportion, uniformly coating the mixed slurry on a metal current collector, and drying to prepare the electrode.
According to an embodiment of the present invention, the conductive agent is selected from at least one of a carbon black-based conductive agent, a carbon fiber, ketjen black, and a carbon nanotube.
According to an embodiment of the present invention, the binder is selected from at least one of sodium carboxymethylcellulose (CMC), styrene Butadiene Rubber (SBR) and polyvinylidene fluoride (PVDF).
According to an embodiment of the present invention, the mass ratio of the hard carbon, the binder and the conductive agent is (60-95) to (1-10) to (1-30), preferably (80-90) to (1-10) to (5-10), for example 80:5:5: 10. 90:3:3:4.
according to an embodiment of the invention, said metallic current collector is selected from copper foil and/or aluminum foil.
The invention also provides application of the hard carbon material, the negative electrode material or the electrode, and the hard carbon material, the negative electrode material or the electrode is preferably used for an energy storage battery.
The invention also provides an energy storage battery which comprises the hard carbon material, the negative electrode material or the electrode.
According to an embodiment of the invention, the energy storage battery is selected from at least one of a lithium ion battery, a sodium ion battery and a potassium ion battery.
According to an exemplary aspect of the invention, when the energy storage battery is a sodium ion battery, the electrode includes a metal current collector and the hard carbon material, wherein the metal current collector is selected from a copper foil and/or an aluminum foil.
According to an exemplary aspect of the invention, when the energy storage battery is a lithium ion battery, the electrode includes a metal current collector and the hard carbon material, wherein the metal current collector is selected from copper foil.
According to an embodiment of the invention, the energy storage battery further comprises an electrolyte.
Preferably, the electrolyte is selected from at least one of ether electrolyte, ester electrolyte, gel electrolyte, solid polymer electrolyte, solid inorganic electrolyte or organic-inorganic composite electrolyte.
Advantageous effects
The method comprises the steps of dissolving soluble carbohydrate serving as a raw material in an acid solution with a certain concentration, raising the temperature, quickly dehydrating to obtain a pre-carbonized precursor, and carbonizing at high temperature in an inert atmosphere to obtain the hard carbon material. The invention takes soluble carbohydrate as raw material, which has wide resource and low cost.
According to the invention, most of water in the carbohydrate can be removed in the acid dehydration and pre-carbonization process, so that the fluidity of the carbon precursor is greatly weakened in the subsequent coking and carbonization process, the directional ordered arrangement of carbon atoms is inhibited, the generation of soft carbon with low crystal face interlayer spacing is reduced, and solid-phase carbonization is realized, so that the hard carbon material with a hard carbon structure which has a relatively disordered structure and large crystal face interlayer spacing is obtained, and the hard carbon structure has a large amount of crystal face interlayer spacing of a sub-nanopore structure and a quasi-hard carbon structure, which can not be accessed by electrolyte.
The method can obtain a pre-carbonization precursor by regulating the type of carbohydrate, the adding amount and concentration of an acid solution and the reaction temperature, and can regulate and control the hard carbon material, such as the aperture of a pore structure and the spacing of crystal planes of a quasi-hard carbon structure, through high-temperature carbonization temperature, heating rate and the like. The hard carbon negative electrode material with high quality/volume specific capacity and excellent rate capability can be obtained by further optimizing parameters, and the promotion of the high-rate charge and discharge capacity of the lithium ion battery and the development of the industrialization of the sodium ion battery are promoted.
The hard carbon material prepared by the method has higher specific capacity and first-turn coulombic efficiency as a negative electrode material, and has quick charge-discharge capacity and excellent cycle stability.
Drawings
Fig. 1 shows a scanning electron micrograph of the hard carbon material after grinding in example 1.
Fig. 2 shows the XRD pattern of the hard carbon material in example 1.
Fig. 3 shows the charge and discharge curves of the assembled sodium ion battery in test example 1.
Fig. 4 shows the rate performance of the assembled sodium ion battery in test example 1.
Fig. 5 shows a charge and discharge curve of the assembled lithium ion battery in test example 2.
Fig. 6 shows the charge and discharge curves of the sodium ion battery in test example 3.
Fig. 7 shows a graph of the cycling specific capacity of the hard carbon material sodium ion battery in test example 4.
Fig. 8 shows a rate comparison of the sodium ion battery in test example 3.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In the following examples, unless otherwise specified, M is mol L -1 。
Example 1
The preparation method of the hard carbon material comprises the following steps: dissolving 4g glucose in 15mL 0.04M dilute sulfuric acid, placing the obtained solution in an oven at 10 deg.C for min -1 The temperature is increased to 180 ℃ at the heating rate and is kept for 4 hours, and the pre-carbonized precursor is obtained. Drying, placing the obtained pre-carbonized precursor into a tube furnace, and heating at 5 deg.C for min in nitrogen atmosphere -1 The temperature is raised to 1000 ℃ at the heating rate, the mixture is carbonized for 2 hours, the mixture is naturally cooled and then is taken out and ground into powder, and the hard carbon material is obtained, and the performance of the hard carbon material is shown in table 1.
The scanning electron microscope of the hard carbon material of this example 1 is shown in fig. 1, and the XRD characterization is shown in fig. 2, where the 002 peak 2 θ =22.5 °, the quasi-hard carbon structure is a layer, the (002) interplanar spacing thereof is 0.394nm, the disordered carbon in the hard carbon material constitutes a sub-nanometer pore structure, and the pore diameter of the pore structure is 0.5nm.
Example 2
Preparing a hard carbon material: dissolving 4g sucrose in 15mL 0.04M dilute sulfuric acid, placing the obtained solution in an oven at 10 deg.C for min -1 The temperature is increased to 180 ℃ at the heating rate and is kept for 4 hours, and the pre-carbonized precursor is obtained. Drying, putting the obtained pre-carbonized precursor into a tube furnace, and heating at 5 ℃ for min under the argon atmosphere -1 The temperature is raised to 1000 ℃ at the heating rate, carbonization is carried out for 2h, the material is taken out after natural cooling and then is put into a nylon ball milling tank for ball milling for 5min, and the hard carbon material is obtained, and the performance of the hard carbon material is shown in table 1.
Example 3
Preparing a hard carbon material: dissolving 4g water soluble starch in 15mL 0.04M diluted phosphoric acid, placing the obtained solution in oven at 10 deg.C for min -1 The temperature is increased to 180 ℃ at the heating rate and is kept for 4 hours, and a pre-carbonized precursor is obtained. Drying, putting the pre-carbonized precursor into a tube furnace, and heating at 5 deg.C for min under nitrogen atmosphere -1 The temperature is raised to 1000 ℃ at the heating rate, the mixture is carbonized for 2 hours, the mixture is taken out after natural cooling and ground into powder, the powder is washed for 2 to 5 times, and the hard carbon material is obtained after drying, and the performance of the hard carbon material is shown in table 1.
Example 4
Preparing a hard carbon material: a hard carbon material was prepared as described in example 2, except that the carbonization temperature in the tube furnace was 900 ℃, and the properties of the prepared hard carbon material were as shown in table 1.
Example 5
Preparing a hard carbon material: dissolving 4g glucose in 15mL 0.04M dilute sulfuric acid, placing the obtained solution in an oven at 10 deg.C for min -1 The temperature is increased to 180 ℃ at the heating rate and is kept for 4 hours, and a pre-carbonized precursor is obtained. Drying, placing the obtained pre-carbonized precursor into a tube furnace in nitrogen atmosphere at 1 deg.C for min -1 At a temperature rise rate of 500 ℃ and subsequently at a temperature of 5 ℃ for a min -1 Heating to 900 ℃ for carbonization for 2h, naturally cooling, taking out, and ball-milling into powder to obtain the hard carbon material, wherein the properties of the hard carbon material are shown in Table 1.
Example 6
Preparing a hard carbon material: 10mL of 0.04M dilute sulfuric acid and 5mL of 0.04M phosphoric acid solution were mixed well. And 4g of trehalose is dissolved in the prepared mixed acid solution, the obtained solution is put into an oven to be dried for 24 hours at the temperature of 80 ℃, and then the temperature is raised to 180 ℃ and kept for 4 hours, so that a pre-carbonized precursor is obtained. Drying, placing the obtained pre-carbonized precursor into a tube furnace, and keeping the temperature at 5 ℃ for min under argon atmosphere -1 The temperature is increased to 900 ℃ at the heating rate, carbonization is carried out for 2h, the mixture is taken out after natural cooling and ball milled into powder, the powder is washed for 3 times and dried to obtain the hard carbon material, and the performance of the hard carbon material is shown in table 1.
Example 7
Preparing a hard carbon material: 2g of pectin is put into 15mL of 0.01M dilute sulfuric acid and stirred and dissolved in an oil bath at 80 ℃. Transferring the solution to an oven to be heated to 180 ℃ after dissolution and preserving heat for 4h to obtain the pre-carbonized precursor.Drying, putting the obtained pre-carbonized precursor into a tube furnace, and heating at 1 deg.C for min under argon atmosphere -1 The temperature is raised to 1000 ℃ at the heating rate, the mixture is carbonized for 2 hours, and the mixture is taken out and ball milled into powder after natural cooling, so that the hard carbon material is obtained, and the performance of the hard carbon material is shown in table 1.
Example 8
Hard carbon materials were prepared as described in example 1, except that the dilute sulfuric acid concentrations were 0.02M, respectively, to prepare hard carbon materials 8, the properties of which are shown in table 1.
Example 9
Hard carbon materials were prepared as described in example 1, except that the dilute sulfuric acid concentrations were 0.08M, respectively, to prepare hard carbon materials 9, the properties of which are shown in table 1.
Comparative example 1
Preparing a hard carbon material: dissolving 4g glucose in 15mL water, placing the solution in an oven at 10 deg.C for min -1 The temperature is increased to 180 ℃ at the heating rate and is kept for 4 hours, and the pre-carbonized precursor is obtained. Drying, putting the pre-carbonized precursor into a tube furnace, and heating at 5 deg.C for min under nitrogen atmosphere -1 The temperature is raised to 1000 ℃ at the heating rate, carbonization is carried out for 2h, the material is taken out after natural cooling and is ball milled into powder, and a comparative hard carbon material 1 is obtained, and the performance of the material is shown in table 1.
Comparative example 2
A hard carbon material was prepared as described in comparative example 1, except that the carbonization temperature in the tube furnace was 1200 c, to obtain comparative hard carbon material 2, the properties of which are shown in table 1.
Comparative example 3
A hard carbon material was prepared as described in example 5, except that 4g of glucose was dissolved in 15mL of water to prepare a solution, and a comparative hard carbon material 3, the properties of which are shown in table 1, was prepared.
The hard carbon materials prepared in examples 2 to 9 above had substantially the same pore structure as in example 1, and the pore diameters of the pore structure were all in the range of 0.35 to 0.7 nm.
The comparative hard carbon materials prepared in comparative examples 1 to 3 have larger volume expansion in the carbonization process due to no acid solution dehydration treatment, the generated pore diameter range is 1 to 3nm, and the (002) crystal plane interlayer spacing in the formed quasi-hard carbon structure is smaller.
Test example 1
And (3) multiplying power testing: the hard carbon materials of examples 1-9, the comparative hard carbon materials of comparative examples 1-2, respectively, were taken and mixed with CMC, SBR, and Super P conductive carbon black at a ratio of 80:5:5:10, coating the mixture on a copper foil, performing vacuum drying to obtain a negative electrode, using a metal sodium sheet as a counter electrode, using Celgard 2325 as a battery diaphragm, and mixing the mixture in a ratio of two and 1M NaPF 6 Sodium/carbon half cells were prepared in a glove box as electrolyte solutions, and these were designated as cell 1A, cell 2A, cell 3A, cell 4A, cell 5A, cell 6A, cell 7A, cell 8A, cell 9A, comparative cell 1A, and comparative cell 2A, respectively.
And (3) testing the charge and discharge performance of the battery, wherein the charge and discharge conditions are as follows: constant current charging and discharging; the current density was 0.02 ag -1 (ii) a The discharge cut-off voltage is 0V; the charge cutoff voltage was 2V. The test results are shown in table 1.
Fig. 3 is a charge-discharge curve of the battery 1.
And (3) rate testing: the batteries were subjected to rate tests at currents of 0.1,0.2,0.5,1,2,5, 10,0.2c, respectively, and the results of the rate tests for batteries 1A, 8A, and 9A are shown in fig. 4, in which 0.04M, 0.02M, and 0.08M correspond to batteries 1A, 8A, and 9A, respectively.
TABLE 1 Properties of hard carbon materials and assembled sodium ion batteries of examples and comparative examples
When glucose is used for preparing the hard carbon material, the hard carbon material prepared without being treated by the acid solution has larger specific surface area and lower capacity and first effect through the comparative example 1 and the example 1.
It is understood from comparative example 2 and example 1 that, when the acid solution treatment is not performed, the specific surface area of the obtained hard carbon material is reduced, but the capacity and the first effect are improved, even if the carbonization temperature is increased.
It can be seen from comparing examples 8 and 9 with example 1 that the gram volume of the hard carbon material produced is affected by the difference in the concentration of the acid solution. When the concentration of the acid solution is between 0.01 and 0.2mol L -1 And the prepared hard carbon material has higher capacity. When the concentration of the acid solution is too high or too low, the gram capacity of the hard carbon material may be reduced.
As can be seen from examples 3, 5 and 6, the hard carbon materials prepared by using different soluble carbohydrates have higher specific surface area, and although the high specific surface area can provide larger sodium ion storage adsorption capacity, the surface of the hard carbon material can partially react irreversibly, so that the first effect (first coulomb efficiency) is reduced.
As can be seen from table 1, in the batteries prepared from the hard carbon materials prepared in examples 1 to 9, the ether electrolyte having a high coulombic efficiency was used as the electrolyte, and although the first efficiency of the batteries was not greatly different, the first efficiency of the batteries was also decreased when the specific surface area of the hard carbon material was increased.
Test example 2
Constant-current charge and discharge test: the hard carbon material of example 1, CMC, SBR and Super P conductive carbon black were mixed at a ratio of 80:5:5:10, coated on a copper foil, vacuum dried to be used as a negative electrode, a metallic lithium sheet as a counter electrode, celgard 2325 as a battery separator, EC + DEC + DMC (1 6 As an electrolyte, a lithium/carbon half cell was prepared, denoted as cell 1B.
And (3) carrying out charge and discharge performance test on the battery 1B, wherein the charge and discharge conditions are as follows: constant current charging and discharging; the current density was 0.02 ag -1 (ii) a The discharge cut-off voltage is 0V; the charge cutoff voltage was 2V. The test results are shown in fig. 5.
Test example 3
Constant current charge and discharge test: the hard carbon material, CMC, SBR and Super P conductive carbon black of comparative example 1 were mixed at a ratio of 80:5:5:10, coating the mixture on a copper foil, performing vacuum drying to obtain a negative electrode, using a metal sodium sheet as a counter electrode, using Celgard 2325 as a battery diaphragm, and mixing the mixture in a ratio of two and 1M NaPF 6 Preparation of sodium/carbon as electrolyteHalf cell, designated comparative cell 1B.
The comparative battery 1B was subjected to a charge and discharge performance test under the following charge and discharge conditions: constant current charging and discharging; the current density was 0.02 ag -1 (ii) a The discharge cut-off voltage is 0V; the charge cutoff voltage was 2V. The test results are shown in fig. 6.
Test example 4
Preparing a negative electrode: referring to test example 1, the hard carbon material of example 4, CMC, SBR and Super P conductive carbon black were taken at 80:5:5:10, coating the mixture on an aluminum foil, drying the mixture in vacuum to be used as a negative electrode, using a metal sodium sheet as a counter electrode, using Celgard 2325 as a battery diaphragm, and using diglyme +1M NaPF 6 As an electrolyte, a sodium/carbon half cell was prepared, denoted as cell 4A'.
And (3) testing the charge and discharge performance of the battery 4A', wherein the charge and discharge conditions are as follows: constant current charging and discharging; the current is 0.5C; the discharge cut-off voltage is 0V; the charge-up cutoff voltage was 2V, and the test results are shown in fig. 7.
Test example 5
Preparing a negative electrode: referring to test example 1, the hard carbon material of example 5 and the comparative hard carbon material 3 of comparative example 3, CMC, SBR and Super P conductive carbon black were taken, respectively, at 80:5:5:10, coating the mixture on an aluminum foil, drying the mixture in vacuum to be used as a negative electrode, using a metal sodium sheet as a counter electrode, using Celgard 2325 as a battery diaphragm, and using diglyme +1M NaPF 6 As electrolyte, a sodium/carbon half cell was prepared, designated as cell 5A 'and comparative cell 3A', respectively.
And (3) testing the charge and discharge performance of the battery 5A 'and the comparative battery 3A', wherein the charge and discharge conditions are as follows: constant current charging and discharging; the current is 0.5C; the discharge cut-off voltage is 0V; the charge cutoff voltage was 2V and the test results are shown in fig. 8, where pre-carbonized represents cell 5A 'and non-pre-carbonized represents comparative cell 3A'.
As can be seen from the rate test and the cycle test of the test examples 4 and 5, when the hard carbon material prepared by the invention is used as a negative electrode material, the battery has better capacity retention rate under different current conditions.
The above description is that of the exemplary embodiments of the invention. However, the scope of protection of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a hard carbon material, comprising the steps of:
(1) Dissolving carbohydrate in an acid solution, quickly heating to evaporate the solvent, and dehydrating or partially dehydrating the carbohydrate to obtain a pre-carbonized precursor;
(2) And (2) carbonizing the precursor prepared in the step (1) at high temperature in an inert atmosphere to obtain the hard carbon material.
2. The method according to claim 1, wherein in the step (1), the carbohydrate is at least one selected from the group consisting of glucose, fructose, sucrose, galactose, lactose, maltose, soluble hemicellulose, pectin, trehalose, raffinose, stachyose, sorbitol, mannitol, xylitol, gluconic acid and water-soluble starch.
Preferably, in the step (1), the acid solution is one or a mixture of two or more selected from sulfuric acid, phosphoric acid, polyphosphoric acid and selenic acid.
Preferably, in the step (1), the concentration of the acid solution is 0.001-0.5 mol L -1 Preferably 0.01 to 0.2mol L -1 。
Preferably, the rapid temperature rise means that the temperature rise rate is 5-50 ℃ for min -1 Heating to the drying temperature and then preserving the heat for a period of time.
Preferably, the drying temperature is 100 to 250 ℃.
Preferably, the holding time is 2 to 24 hours.
3. The method according to claim 1 or 2, wherein in the step (2), the temperature of the high-temperature carbonization is 600 to 2000 ℃; the heat preservation time is 0.5 to 20 hours at the high-temperature carbonization temperature.
Illustratively, the temperature of the high-temperature carbonization is 800-1500 ℃, and the holding time is 1-10 h.
Preferably, the high-temperature carbonization comprises a temperature rise stage and a heat preservation treatment, and preferably, after the temperature is raised to the temperature of the high-temperature carbonization, the heat preservation treatment is carried out.
Preferably, the temperature raising stage is to raise the temperature to the temperature for high-temperature carbonization at a certain temperature raising rate.
Preferably, the heating rate is 0.1-20 ℃ min -1 Preferably 0.5 to 10 ℃ for min -1 。
4. The production method according to any one of claims 1 to 3, characterized by further comprising: (3) Pulverizing the hard carbon material prepared in the step (2) to a suitable particle size.
Preferably, the hard carbon material has a particle size of 0.1 to 50 μm, preferably 1 to 30 μm.
5. A hard carbon material comprising a quasi-graphitic structure and a pore structure composed of disordered carbon.
Preferably, the quasi-graphite structure is layered, wherein the interlayer spacing of a (002) crystal face is 0.35-0.7 nm; preferably 0.35 to 0.5nm.
Preferably, the size of the pore structure composed of the disordered carbon is 0.35-0.7 nm; preferably 0.4 to 0.6nm.
6. The hard carbon material according to claim 5, which is produced by the above production method.
Preferably, the gram capacity of the hard carbon material is 200-650 mAh g -1 。
Preferably, the hard carbon material has a particle size of 0.1 to 50 μm, preferably 1 to 30 μm.
Preferably, the hard carbon material has a specific surface area of 0.1 to 1000m 2 g -1 Preferably 0.1 to 200m 2 g -1 。
7. An anode material comprising the hard carbon material of claim 5 or 6.
8. An electrode comprising the hard carbon material of claim 5 or 6 and/or the negative electrode material of claim 7.
9. Use of the hard carbon material of claim 5 or 6, the negative electrode material of claim 7 or the electrode of claim 8, preferably in an energy storage battery.
10. An energy storage battery comprising the hard carbon material of claim 5 or 6, the negative electrode material of claim 7, or the electrode of claim 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050207962A1 (en) * | 2004-03-18 | 2005-09-22 | Tda Research, Inc. | Porous carbons from carbohydrates |
| CN109921018A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material |
| CN110148734A (en) * | 2019-05-30 | 2019-08-20 | 蜂巢能源科技有限公司 | Hard carbon cathode material and its preparation method and application |
| CN113292065A (en) * | 2021-05-25 | 2021-08-24 | 北京理工大学 | Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof |
| CN113903896A (en) * | 2021-09-28 | 2022-01-07 | 上海普澜特夫精细化工有限公司 | Secondary particle hard carbon composite material and preparation method and application thereof |
-
2022
- 2022-07-25 CN CN202210880395.3A patent/CN115360348A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050207962A1 (en) * | 2004-03-18 | 2005-09-22 | Tda Research, Inc. | Porous carbons from carbohydrates |
| CN109921018A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material |
| CN110148734A (en) * | 2019-05-30 | 2019-08-20 | 蜂巢能源科技有限公司 | Hard carbon cathode material and its preparation method and application |
| CN113292065A (en) * | 2021-05-25 | 2021-08-24 | 北京理工大学 | Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof |
| CN113903896A (en) * | 2021-09-28 | 2022-01-07 | 上海普澜特夫精细化工有限公司 | Secondary particle hard carbon composite material and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116062735A (en) * | 2023-03-20 | 2023-05-05 | 四川兴储能源科技有限公司 | Hard carbon prepared by non-sintering dehydration carbonization method and application thereof |
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