CN113381013A - Sodium ion battery coal-based hard carbon negative electrode material and preparation method and application thereof - Google Patents
Sodium ion battery coal-based hard carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- CN113381013A CN113381013A CN202110630727.8A CN202110630727A CN113381013A CN 113381013 A CN113381013 A CN 113381013A CN 202110630727 A CN202110630727 A CN 202110630727A CN 113381013 A CN113381013 A CN 113381013A
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- ion battery
- sodium
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- 239000003245 coal Substances 0.000 title claims abstract description 99
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 77
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 75
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 52
- 238000003763 carbonization Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000007833 carbon precursor Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- 239000003077 lignite Substances 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 239000002802 bituminous coal Substances 0.000 claims description 18
- 239000003476 subbituminous coal Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- 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 5
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
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- 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 abstract description 14
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- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 7
- 239000003830 anthracite Substances 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 7
- 239000013081 microcrystal Substances 0.000 description 7
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
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- 239000010405 anode material Substances 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 239000003610 charcoal Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, and provides a preparation method of a coal-based hard carbon negative electrode material of a sodium ion battery, which comprises the following steps: firstly, performing deliming treatment on raw material coal to obtain a carbon precursor; and then placing the carbon precursor in an inert atmosphere for high-temperature carbonization, and performing programmed cooling to obtain the coal-based hard carbon material. According to the invention, through a deashing means, the coal is deashed, but volatile matters, N, S, O and other heteroatoms are retained, so that the safety of the material is improved, and the conductivity of the material is considered at the same time. The coal-based hard carbon material prepared by the method is used as a negative electrode material of the sodium-ion battery, and has high sodium storage capacity and first coulombic efficiency.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a coal-based hard carbon negative electrode material of a sodium ion battery, and a preparation method and application thereof.
Background
The sodium has the advantages of abundant reserves, wide distribution and low price, and can solve the problems of high price and limited resources of the lithium ion battery. Meanwhile, the experience of the lithium ion battery accumulated in the aspects of battery technology and technology can be used for reference of the sodium ion battery. Therefore, sodium ion batteries are considered to be one of the most promising large-scale electrochemical energy storage systems at present.
The negative electrode material is used as a key material of the sodium ion battery, and the development of the negative electrode material with high performance and low cost is an important step for promoting the commercialization process of the sodium ion battery. Currently, sodium-electric anode materials are classified into alloys (phosphorus, silicon, tin, lead, etc.), conversion types (metal oxides, metal sulfides, etc.), and intercalation types (titanium-based oxides and carbon materials) according to the difference of energy storage mechanisms. However, alloys and conversion materials have a volume expansion problem, which leads to the continuous capacity attenuation in the charge-discharge cycle process; the titanium-based material has poor conductivity, so the electrochemical rate performance of the material needs to be improved. These inherent limitations due to the nature of the material itself make them difficult to use commercially. The carbon material has the advantages of rich source, low price, low potential, strong conductivity and strong structural stability, and becomes one of the most practical negative electrode materials of sodium ions. The lithium battery graphite cathode and the highly ordered graphite soft carbon cathode have lower sodium storage capacity because the ionic radius of sodium ions is larger than that of lithium ions. The hard carbon material has rich defects and heteroatoms, graphite microcrystals with large interlayer spacing, a large number of active sites for storing sodium, and the like, and is suitable for serving as a negative electrode material of a sodium-ion battery.
The hard charcoal is mainly prepared by high-temperature carbonization of biomass, high molecular polymer, coal and other raw materials. The coal is a high-quality raw material for preparing the carbon material due to high carbon content, developed aromatic structure, low price and rich resources. And the types of coal are various, and can be divided into anthracite, bituminous coal (subbituminous coal), lignite and peat according to the degree of deterioration. The carbon content of the anthracite exceeds 90 percent, the carbon material obtained by carbonization belongs to soft carbon, the graphite interlamellar spacing is small, the content of heteroatoms is low, and the coal with low metamorphic grade can form a coal-based hard carbon material with larger graphite interlamellar spacing, richer heteroatom content and defect structure through high-temperature carbonization, and is more suitable to be used as a cathode material of a sodium-ion battery.
Disclosure of Invention
The invention solves the prior art problems that inorganic mineral substances contained in coal with low metamorphism degree in the prior art can be converted into ash residue during high-temperature treatment, and the ash generally has poor electrical conductivity and no electrochemical activity, so that the sodium storage performance of the material is reduced. Fe2O3、Cr2O3The ash components are dissolved out from the hard carbon negative electrode in the sodium ion battery, which not only catalyzes the decomposition of electrolyte and reduces the coulombic efficiency, but also easily causes the problems of self-discharge effect and the like.
Specifically, the invention provides the following technical scheme:
in a first aspect, the embodiment of the invention provides a coal-based hard carbon negative electrode material of a sodium ion battery, wherein the coal-based hard carbon material of the sodium ion battery is granular, and the interplanar spacing d002A value of 0.2nm or more, a preferred interplanar spacing d002Values of 0.2 to 0.5nm, more preferably the interplanar spacing d002The value is 0.364-0.384 nm.
Preferably, the sodium ion battery coal-based hard carbon material AG/ADValues of 0.1 to 0.6, more preferably AG/ADThe value is 0.21-0.49.
Preferably, the sodium ion battery coal-based hard carbon material LcValues of 1-4nm, more preferably LcThe value is 2.11-2.60 nm; l isaValues of 0.5-2.5nm, more preferably LaThe value is 1.75-2.18 nm.
Preferably, the average particle size of the coal-based hard carbon negative electrode material of the sodium-ion battery is 28-470 microns.
Preferably, the sodium ion battery coal-based hard carbon negative electrode material is obtained by performing deashing treatment, carbonization treatment and programmed cooling treatment on raw material coal, wherein the raw material coal is one or more of bituminous coal, sub-bituminous coal and lignite, and the preferred coal is lignite.
Preferably, the programmed cooling treatment is carried out at 1-5 ℃ for min-1The temperature is reduced to 15-30 ℃ at the speed rate.
Preferably, the deliming treatment is 2-step deliming treatment by using acid, preferably, the 2-step deliming treatment is treatment by using hydrochloric acid, nitric acid or sulfuric acid, wherein the acid used in the 2-step deliming treatment can be the same or different.
In a second aspect, the invention provides a preparation method of a coal-based hard carbon negative electrode material of a sodium ion battery, which comprises the following steps:
step 1: the raw material coal is crushed, sieved, placed in a deashing solution for treatment, washed to be neutral, and dried to obtain a precursor.
Step 2: and (3) carrying out high-temperature carbonization on the precursor obtained in the step (1) under the protection of inert gas, and carrying out programmed cooling to 15-30 ℃ to obtain the coal-based hard carbon negative electrode material of the sodium ion battery.
Preferably, the raw material coal is one or more of bituminous coal, sub-bituminous coal and lignite, and more preferably, the raw material coal is lignite.
Preferably, in the preparation method of the sodium ion battery coal-based hard carbon negative electrode material, in the step 1, the treatment in the deliming solution is 2-step deliming treatment by using acid; preferably, the 2-step deashing treatment is carried out by using hydrochloric acid, hydrofluoric acid, nitric acid or sulfuric acid, wherein the acids used in the 2-step deashing treatment can be the same or different.
Preferably, in the preparation method of the coal-based hard carbon negative electrode material of the sodium ion battery, in step 1, the dosage of the deashing solution is as follows: and (3) deashing the coal by using 10-30mL of acid per gram of coal.
Preferably, in the preparation method of the sodium ion battery coal-based hard carbon negative electrode material, in the step 2, the high-temperature carbonization temperature is 1000-.
Preferably, in the preparation method of the sodium ion battery coal-based hard carbon negative electrode material, in the step 2, the inert gas used for carbonization is at least one of argon and argon.
Preferably, in the preparation method of the sodium ion battery coal-based hard carbon negative electrode material, in the step 2, the introduction flow rate of the inert gas for carbonization is 30-600cc min-1。
Preferably, the sodium ion battery coal-based hard carbon negative electrodeThe preparation method of the material comprises the step 2 of heating the mixture at 1-5 ℃ for min-1The temperature is raised to 1000-1600 ℃ and kept for 1-4h, more preferably 1-5 ℃ for min-1The temperature was raised to 1350-.
Preferably, in the preparation method of the sodium ion battery coal-based hard carbon negative electrode material, in the step 2, the cooling process adopts program cooling, and the temperature is 1-5 ℃ for min-1Cooling to 15-30 deg.C.
In a third aspect, the invention provides an electrode plate made of the coal-based hard carbon negative electrode material of the second aspect, which is characterized by further comprising a conductive agent, a binder and a current collector.
Preferably, the binder on the negative electrode plate comprises one or more of sodium carboxymethylcellulose, sodium alginate, polyacrylic acid, PVDF and LA 133.
Preferably, the conductive agent on the negative electrode plate comprises one or more of carbon nanotubes, carbon fibers, graphene, acetylene black and SuperP.
In a fourth aspect, the invention provides a sodium-ion battery comprising the coal-based hard carbon negative electrode plate in the third aspect.
The beneficial effects of the invention include:
(1) the deashing technology of the invention can effectively remove the ash in the coal, and is beneficial to improving the energy density and the safety of the battery.
(2) The setting of the carbonization procedure can effectively regulate the disorder degree, the defect structure and the heteroatom content of the coal-based hard carbon, and is beneficial to realizing the preparation of the high-performance coal-based hard carbon cathode material.
(3) The preparation method of the coal-based hard carbon cathode material of the sodium ion battery is simple, the raw materials are easy to obtain, the carbon yield is high, the cost is low, and the method is suitable for industrial mass production.
Drawings
FIG. 1 is an XRD spectrum of YM-1000, YM-1200, YM-1400 and YM-1600 in preparation example 4;
FIG. 2 is a Raman spectrum of YM-1000, YM-1200, YM-1400 and YM-1600 in preparation example 4;
FIG. 3 is an XRD spectrum of CYM-1000, CYM-1200, CYM-1400 and CYM-1600 in preparative example 5;
FIG. 4 is a Raman spectrum of CYM-1000, CYM-1200, CYM-1400 and CYM-1600 from preparation example 5;
FIG. 5 is an XRD spectrum of HM-1000, HM-1200, HM-1400 and HM-1600 in preparation example 6;
FIG. 6 is a Raman spectrum of HM-1000, HM-1200, HM-1400 and HM-1600 in preparation example 6;
FIG. 7 is a graph showing the first charge and discharge curves of EP-YM-1000, EP-YM-1200, EP-YM-1400 and EP-YM-1600 in application example 1;
FIG. 8 is a graph showing a comparison of first charge and discharge curves of EP-YM-0-1400 in comparative application example 1 and EP-YM-1400 in application example 1;
FIG. 9 is a graph showing rate capability of EP-YM-1000, EP-YM-1200, EP-YM-1400 and EP-YM-1600 in application example 1;
FIG. 10 is a graph showing the first charge and discharge curves of EP-CYM-1000, EP-CYM-1200, EP-CYM-1400 and EP-CYM-1600 in application example 2;
FIG. 11 is a graph comparing the first charge-discharge curves of EP-CYM-0-1400 in comparative application example 2 and EP-CYM-1400 in application example 2;
FIG. 12 is a graph of the rate capability of EP-CYM-1000, EP-CYM-1200, EP-CYM-1400 and EP-CYM-1600 in application example 2;
FIG. 13 is a graph showing the first charge and discharge curves of EP-HM-1000, EP-HM-1200, EP-HM-1400 and EP-HM-1600 in application example 3;
FIG. 14 is a graph comparing first charge and discharge curves of EP-HM-0-1400 in application comparative example 3 and EP-HM-1400 in application example 3;
FIG. 15 is a graph of the rate capability of EP-HM-1000, EP-HM-1200, EP-HM-1400 and EP-HM-1600 in application example 3.
Detailed Description
The invention relates to the technical field of sodium ion batteries, and provides a preparation method of a coal-based hard carbon negative electrode material of a sodium ion battery, which comprises the following steps: firstly, performing deliming treatment on raw material coal to obtain a carbon precursor; and then placing the carbon precursor in an inert atmosphere for high-temperature carbonization, and performing programmed cooling to obtain the coal-based hard carbon material. According to the invention, through a deashing means, the coal is deashed, but volatile matters, N, S, O and other heteroatoms are retained, so that the safety of the material is improved, and the conductivity of the material is considered at the same time. The coal-based hard carbon material prepared by the method is used as a negative electrode material of the sodium-ion battery, and has high sodium storage capacity and first coulombic efficiency.
In the prior art, when coal is adopted to prepare the hard carbon negative electrode material of the sodium ion battery, the coal with low metamorphism degree causes residual ash (converted from inorganic mineral substances in the coal) during high-temperature treatment so as to reduce the sodium storage performance of the battery material. The invention adopts the methods of deashing and high-temperature carbonization to prepare the coal-based hard carbon negative electrode material. The ash content in the coal can be effectively removed through acid washing treatment, and the energy density and the safety of the battery can be improved. The disorder degree and the heteroatom type of the high-temperature carbonization adjustable material and the coal-based hard carbon can show high reversible specific capacity and quick sodium storage performance. The material has rich raw material reserves, low cost and high carbon yield, and is suitable for large-scale production.
In order to solve the above-mentioned problems of the prior art, in a specific embodiment, the present invention provides a sodium ion battery negative electrode material, which is characterized in that the material is a coal-based hard carbon material, coal is used as a raw material, a deliming solution is adopted to perform deliming treatment, drying is performed, and then high temperature carbonization is performed under an inert atmosphere to prepare the sodium ion battery negative electrode material.
Wherein the coal comprises one or a mixture of more of bituminous coal, sub-bituminous coal and lignite.
Wherein, the deliming solution comprises one or a mixture of any more of hydrochloric acid, hydrofluoric acid, nitric acid and sulfuric acid.
In another specific embodiment, the invention also provides a preparation method of the coal-based hard carbon negative electrode of the sodium ion battery, which is characterized by comprising the following steps:
(1) firstly, grinding and crushing coal by a mortar, and then sieving the crushed coal by a sieve with 50-300 meshes.
(2) Treating the coal obtained in the last step for 6-12h by acid in 2 steps, wherein the total amount of acidThe mass ratio of the dosage to the coal is 10-30mL g-1. And then the sample is subjected to vacuum filtration, water washing and neutral, and then the sample is placed in a 50 ℃ blast oven for drying for 24 hours.
(3) Putting the sample obtained in the previous step into a graphite boat, placing the graphite boat in a tube furnace, introducing argon as inert gas, and controlling the flow rate of carrier gas to be 60cc min-1Then at 3 ℃ for min-1Heating to 1000-1600 deg.c and staying for 2 hr. And (3) cooling to 15-30 ℃ by adopting a program, and then taking out from the tubular furnace to obtain the coal-based hard carbon cathode material of the sodium ion battery. The process of program cooling is adopted to ensure that the stress change generated by the temperature change on the material is smooth, and the material shrinkage process is uniform.
The invention provides a coal-based hard carbon negative electrode plate which comprises the coal-based hard carbon material, a conductive agent, a binder and a current collector.
The coal-based hard carbon material on the negative pole piece comprises one or more of bituminous coal-based hard carbon, sub-bituminous coal-based hard carbon and brown coal-based hard carbon.
The binder on the negative pole piece comprises one or more of sodium carboxymethylcellulose, sodium alginate, polyacrylic acid, PVDF and LA133, but is not limited thereto.
The conductive agent on the negative electrode plate comprises one or more of carbon nano tube, carbon fiber, graphene, acetylene black and Super P, but is not limited to the above.
In addition, the invention provides a sodium ion battery comprising the coal-based hard carbon negative pole piece.
The following examples and comparative examples, unless otherwise stated, were prepared as shown in table 1 below:
TABLE 1 information on the raw materials used in the present invention
For a better understanding of the technical solutions of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings and specific examples.
I. Preparation examples
Preparation of example 1
Firstly, pouring bituminous coal into a mortar for crushing, sieving by a 100-mesh sieve, weighing 3g of bituminous coal, pouring into a conical flask, adding 15mL of 4mol L-1Continuously stirring in hydrochloric acid for 6h, carrying out vacuum filtration, washing with water to neutrality, and drying the sample in a forced air oven at 50 ℃ for 24 h. And pouring the dried bituminous coal into a plastic bottle, adding 15mL of 10 wt% hydrofluoric acid, continuously stirring for 6h, carrying out vacuum filtration, washing with water to neutrality, placing in a 50 ℃ forced air oven, and drying for 24h, wherein the obtained sample is named as YM-1.
Preparation of example 2
Firstly, pouring sub-bituminous coal into a mortar for crushing, sieving by a 100-mesh sieve, weighing 3g of the crushed sub-bituminous coal, pouring the weighed sub-bituminous coal into a conical flask, and adding 15mL of 4mol L-1Continuously stirring in hydrochloric acid for 6h, carrying out vacuum filtration, washing with water to neutrality, and drying the sample in a forced air oven at 50 ℃ for 24 h. And pouring the dried sub-bituminous coal into a plastic bottle, adding 15mL of 10 wt% hydrofluoric acid, continuously stirring for 6h, carrying out vacuum filtration and water washing until the mixture is neutral, placing the mixture in a 50 ℃ blast oven for drying for 24h, and naming the obtained sample as CYM-1.
Preparation of example 3
Firstly, pouring lignite into a mortar for crushing, sieving by a 100-mesh sieve, weighing 3g of lignite, pouring the weighed 3g of lignite into a conical flask, and adding 15mL of 4mol L of lignite-1Continuously stirring in hydrochloric acid for 6h, carrying out vacuum filtration, washing with water to neutrality, and drying the sample in a forced air oven at 50 ℃ for 24 h. And pouring the dried lignite into a plastic bottle, adding 15mL of 10 wt% hydrofluoric acid, continuously stirring for 6h, carrying out vacuum filtration and water washing until the lignite is neutral, placing the lignite in a 50 ℃ forced air oven for drying for 24h, and naming the obtained sample as HM-1.
Preparation of example 4
Weighing 4g of YM-1 prepared in preparation example 1, placing into four graphite boats, placing into a tube furnace, introducing argon gas, and selecting a carrier gas flow rate of 60cc min-1Then at 3 ℃ for min-1Respectively heating to 1000 deg.C, 1200 deg.C, 1400 deg.C and 1600 deg.C, standing for 2 hr, and heating at 2 deg.C for min-1And cooling to room temperature to obtain the sodium ion battery bituminous coal-based hard carbon negative electrode material. The resulting samples were designated YM-1000, YM-1200, YM-1400 and YM-1600, respectively.
The sample obtained as described above was subjected to XRD, raman spectroscopy and XPS characterization, and the test results thereof are shown in fig. 1, fig. 2, table 2 and table 3 below.
Wherein, the model number and the test condition of the XRD test instrument are as follows:
the XRD data herein were measured on an X' Pert3 Powder X-ray diffractometer manufactured by the company PANALYTICAL B.V. at a test voltage of 40 KV; the anode material is a Cu target; k alpha excitation; sweeping speed (step 0.02626 DEG, speed 0.1694 DEG s)-1) (ii) a The scanning range 2 θ is 10 ° to 90 °.
The raman spectroscopy test instrument models and conditions were as follows:
the instrument used for Raman testing herein was a DRX-type micro Raman spectrometer from Thermo Fisher Scientific, with a visible lasing wavelength of 532 nm.
XPS test instrument models and conditions were as follows:
a series of samples was analyzed using a multifunctional surface analyzer model ESCALB 250 from Thermofish VG Scientific, Inc. Monochromatic Al K alpha is 1486.6eV as excitation source, and energy is 1486.6 eV. The binding energy of the sample was corrected for the central peak of C1s (284.6 eV).
The graphite crystallite interlamellar spacings d of the above-described example samples of the present invention are shown in FIG. 1 and Table 2 below002A value in the range of 0.364-0.381nm, LcA value of 2.13-2.60nm, LaThe value is 1.75-2.13 nm; wherein, the graphite microcrystal interlayer spacing of YM-1000, YM-1200, YM-1400 and YM-1600 is 0.381, 0.374, 0.370 and 0.364nm respectively. The distance between the graphite microcrystal layers is gradually reduced along with the increase of the carbonization temperature. In addition, LaAnd LcThe value gradually increases and the graphite crystallite size gradually increases.
A of the above example samples of the present invention is shown in FIG. 2 and Table 2 belowG/ADThe value is 0.27-0.49, wherein, with increasing carbonization temperature, A of YM-1000, YM-1200, YM-1400 and YM-1600G/ADRespectively 0.27, 0.29, 0.44 and 0.49, and gradually increases, and the defect degree of the material gradually decreases.
Preparation of example 5
Weighing 4g of CYM-1 prepared in preparation example 2, respectively placing the CYM-1 into four graphite boats, placing the graphite boats into a tube furnace, introducing argon, and selecting the flow rate of carrier gas for 60cc min-1Then at 3 ℃ for min-1Respectively heating to 1000 deg.C, 1200 deg.C, 1400 deg.C and 1600 deg.C, standing for 2 hr, and heating at 2 deg.C for min-1And cooling to room temperature to obtain the sodium ion battery subbituminous coal-based hard carbon negative electrode material. The resulting samples were designated CYM-1000, CYM-1200, CYM-1400 and CYM-1600, respectively.
The sample obtained as described above was subjected to XRD measurement, raman spectroscopy and XPS measurement, and the results thereof are shown in the following fig. 3, fig. 4, table 2 and table 3. The measuring apparatus and conditions were the same as those in preparation example 4.
The graphite crystallite interlamellar spacings d of the above-described example samples of the present invention are shown in FIG. 3 and Table 2 below002The value is in the range of 0.364-0.384nm, LcThe value is 2.13-2.56nm, LaThe value is 1.77-2.18 nm; wherein, the graphite microcrystal interlamellar spacing of CYM-1000, CYM-1200, CYM-1400 and CYM-1600 is 0.380 nm, 0.377 nm, 0.372 nm and 0.365nm respectively. The graphite layer spacing gradually decreases as the carbonization temperature increases. In addition, LaAnd LcThe value gradually increases and the graphite crystallite size gradually increases.
A of the above example samples of the present invention is shown in FIG. 4 and Table 2 belowG/ADThe value is 0.26-0.44, wherein, with the increase of the carbonization temperature, A of CYM-1000, CYM-1200, CYM-1400 and CYM-1600G/ADRespectively 0.26, 0.30, 0.38 and 0.44, and the defect degree of the material is gradually reduced in an increasing trend.
Preparation of example 6
Weighing 4g of HM-1 in preparation example 3, respectively placing into four graphite boats, placing into a tube furnace, introducing argon, and selecting a carrier gas flow rate of 60cc min-1Then at 3 ℃ for min-1Respectively heating to 1000 deg.C, 1200 deg.C, 1400 deg.C and 1600 deg.C, standing for 2 hr, and heating at 2 deg.C for min-1And cooling to room temperature to obtain the brown coal-based hard carbon negative electrode material of the sodium ion battery. The resulting samples were designated HM-1000, HM-1200, HM-1400 and HM-1600, respectively.
The XRD test, the raman spectrum test, and the XPS test were performed on the samples obtained as described above, and the test results are shown in fig. 5, fig. 6, table 2, and table 3. The measuring apparatus and conditions were the same as those in preparation example 4.
As shown in FIG. 5 and Table 2, the graphite crystallite interlamellar spacings d of the above-described example samples of the present invention002The value is in the range of 0.368-0.384nm, LcThe value is 2.11-2.46nm, LaThe value is 1.80-2.07 nm; wherein, the graphite microcrystal interlayer spacing of HM-1000, HM-1200, HM-1400 and HM-1600 is 0.384, 0.381, 0.376 and 0.368nm respectively. The graphite microcrystal layer spacing is gradually reduced along with the increase of the carbonization temperature. In addition, LaAnd LcThe value gradually increases and the graphite crystallite size gradually increases. In particular, the graphite crystallite interlamellar spacing of the brown coal-based hard carbon is always larger than that of the bituminous coal-based hard carbon and the subbituminous coal-based hard carbon at the same carbonization temperature.
As shown in FIG. 6 and Table 2, A of the above-mentioned example sample of the present inventionG/ADThe value is 0.21-0.40, wherein, with increasing carbonization temperature, A of HM-1000, HM-1200, HM-1400 and HM-1600G/ADRespectively 0.21, 0.24, 0.28 and 0.40, and gradually increases, and the defect degree of the material gradually decreases. Compared with a bituminous coal group and a sub-bituminous coal group, the brown coal group has the lowest graphitization degree and has more abundant defect structures at the same carbonization temperature. The modification degree of the lignite is low, the lignite contains abundant heteroatoms, and the ordered arrangement of graphite microcrystals in the carbonization process is inhibited.
TABLE 2 structural parameters of YM-1000, YM-1200, YM-1400, YM-1600, CYM-1000, CYM-1200, CYM-1400, CYM-1600, HM-1000, HM-1200, HM-1400 and HM-1600
TABLE 3 results of XPS analysis and elemental analysis of YM-1000, YM-1200, YM-1400, YM-1600, HM-1000, HM-1200, HM-1400 and HM-1600
Preparation of comparative example 1
Anthracite is poured into a mortar for crushing and is sieved by a 100-mesh sieve, and the obtained sample is named as WYM-0.
Preparation of comparative example 2
Firstly, pouring anthracite into a mortar for crushing, sieving by a 100-mesh sieve, weighing 3g of anthracite, pouring into a conical flask, adding 15mL of 4mol L-1Continuously stirring in hydrochloric acid for 6h, carrying out vacuum filtration, washing with water to neutrality, and drying the sample in a forced air oven at 50 ℃ for 24 h. And pouring the dried anthracite into a plastic bottle, adding 15mL of 10 wt% hydrofluoric acid, continuously stirring for 6h, carrying out vacuum filtration, washing with water to neutrality, placing in a 50 ℃ forced air oven, and drying for 24h, wherein the obtained sample is named as WYM-1.
Preparation of comparative example 3
Bituminous coal was poured into a mortar for pulverization and sieved through a 100-mesh sieve, and the obtained sample was named YM-0.
Preparation of comparative example 4
Weighing 1g of YM-0 prepared in comparative example 3, respectively placing in four graphite boats, placing in a tube furnace, introducing argon, and selecting carrier gas flow rate for 60cc min-1Then at 3 ℃ for min-1Heating to 1400 deg.C, standing for 2 hr, and heating at 2 deg.C for min-1And cooling to room temperature to obtain the sodium ion battery bituminous coal-based hard carbon negative electrode material, and naming the obtained material as YM-0-1400.
Preparation of comparative example 5
The subbituminous coal was poured into a mortar for pulverization and sieved through a 100 mesh sieve, and the obtained sample was named CYM-0.
Preparation of comparative example 6
Weighing 1g of CYM-0 prepared in comparative example 5, respectively loading into four graphite boats, placing in a tube furnace, introducing argon, and selecting a carrier gas flow rate of 60cc min-1Then at 3 ℃ for min-1Heating to 1400 ℃, staying for 2h,followed by a heating at 2 ℃ for min-1And cooling to room temperature to obtain the sodium ion battery subbituminous coal-based hard carbon negative electrode material, and naming the obtained material as CYM-0-1400.
Preparation of comparative example 7
The lignite was poured into a mortar for pulverization and sieved through a 100-mesh sieve, and the obtained sample was named HM-0.
Preparation of comparative example 8
Weighing 1g of HM-0 in preparation comparative example 7, respectively placing in four graphite boats, placing in a tube furnace, introducing argon, and selecting carrier gas flow rate for 60cc min-1Then at 3 ℃ for min-1Heating to 1400 deg.C, standing for 2 hr, and heating at 2 deg.C for min-1And cooling to room temperature to obtain the brown coal-based hard carbon cathode material of the sodium ion battery, and naming the obtained material as HM-0-1400.
The samples obtained in preparation examples 1, 2 and 3 and preparation comparative examples 1, 2, 3, 5 and 7 described above were subjected to industrial analysis of coal samples before and after deliming according to the industrial analysis method of national standard GBT2122008 coal, and the mineral composition of the above products was analyzed using an X-ray fluorescence spectrum analyzer (XRF, S8 TIGER, Bruker), and the results are shown in tables 4 and 5. It can be obviously seen that the ash content reduction of samples WYM-1, YM-1, CYM-1 and HM-1 subjected to acid pickling treatment by hydrochloric acid and hydrofluoric acid and subjected to ash removal treatment is over 90% compared with that of samples WYM-0, YM-0, CYM-0 and HM-0 which are not subjected to ash removal treatment, and the treatment method can effectively remove ash. Wherein HM-0 and CYM-0 have loose structures, so that the contact between acid and ash is more sufficient, and therefore, the deashing efficiency of HM-1 and CYM-1 is higher.
The elements contained in the prepared material were quantitatively analyzed by an Element analyzer (Vario EL) of Germany Element. The results of elemental analysis of the samples obtained in the above-described production examples 1, 2, 3 and production comparative example 2 are shown in the following table 4. As can be seen from Table 4, WYM-1, YM-1, CYM-1 and HM-1 are mainly based on carbon and contain small amounts of oxygen, hydrogen, nitrogen and sulfur elements. The carbon content of the prepared coal-based hard carbon material is gradually increased and the oxygen content is gradually reduced along with the sequential increase of the coal deterioration degree from anthracite to bituminous coal, sub-bituminous coal and lignite. HM-1 has the lowest carbon content and the highest oxygen content, and is mainly due to the fact that the molecular structure of the lignite aromatic ring is small, and the number of unstable aromatic hydrocarbon side chains and oxygen-containing functional groups is large.
TABLE 4 results of the Industrial analysis before and after deliming of coal and the elemental analysis after deliming
TABLE 5 results of X-ray fluorescence spectrum analysis before and after coal deliming
Application examples
Application example 1
YM-1000, YM-1200, YM-1400 and YM-1600 in preparation example 4 were used as active materials for preparing a negative electrode of a sodium ion battery, and electrochemical charge and discharge performance tests were performed thereon.
The specific battery preparation process is as follows: the active substance, the carbon nano tube and the sodium carboxymethyl cellulose binder are mixed according to the mass ratio of 8:1:1 to prepare slurry. Firstly, weighing the sodium carboxymethylcellulose binder in a glass bottle, then mixing and grinding the active substance and the carbon nano tube, adding the mixture into the glass bottle, and mechanically stirring for 12 hours to prepare uniform slurry. The obtained slurry is coated on a copper foil current collector by using a coating machine, then is transferred into an air-blowing drying oven for drying at 50 ℃ for 2h, and is further transferred into a vacuum drying oven for drying at 100 ℃ for 12 h. And cutting the dried pole piece into a circular sheet with the diameter of 12mm, and naming the circular sheet as the YM-1 electrode. The electrode tabs are then transferred into a glove box and assembled into a battery. The sodium ion half cell was assembled in an argon atmosphere glove box using a glass fiber membrane (Whatman F) as a separator and 1M NaPF6The solution of ethylene carbonate and diethyl carbonate dissolved in 1L volume ratio of 1:1 is used as electrolyte, and metal sodium is used as a counter electrode to assemble the CR2032 button cell. The resulting cells were designated EP-YM-1000, EP-YM-1200, EP-YM-1400 and EP-YM-1600, respectively.
For the cell prepared in application example 1 described above, 0.02A g-1The first constant current charge and discharge test is performed at current density, and the test result is shown in fig. 7; at 0.02, 0.05, 0.1, 0.2, 0.5A g-1The current density of (3) is tested, the charging and discharging voltage window is 0.01-3.00V, and the test result is shown in figure 9. As can be seen from fig. 7, at 0.02A g-1Compared with EP-YM-1000, EP-YM-1200 and EP-YM-1600, EP-YM-1400 shows better electrochemical performance at the current density of (A). The specific first charge capacity of EP-YM-1400 is 317.5mA hr g-1The first coulombic efficiency was 80%. As can be seen in fig. 9, at 1A g-1Under the high current density, the reversible specific capacity of the optimal sample EP-YM-1400 is 57.1mA h g-1。
Application example 2
CYM-1000, CYM-1200, CYM-1400 and CYM-1600 in preparation example 5 were used as active materials for preparing sodium ion battery negative electrodes, and subjected to electrochemical charge-discharge performance tests, and the obtained batteries were named EP-CYM-1000, EP-CYM-1200, EP-CYM-1400 and EP-CYM-1600, respectively. The procedure and test method were the same as in application example 1.
The first constant current charge and discharge test results of the battery prepared in the above application example 2 are shown in fig. 10; at 0.02, 0.05, 0.1, 0.2, 0.5A g-1The rate capability of the battery is tested under the current density, the charging and discharging voltage window is 0.01-3.00V, and the test result is shown in figure 12. As can be seen from FIG. 12, EP-CYM-1400 shows better rate performance than EP-CYM-1000, EP-CYM-1200 and EP-CYM-1600. As can be seen from fig. 10, at 0.02A g-1At the current density of (2), the first charge specific capacity of EP-CYM-1400 is 326.1mA h g-1The first coulombic efficiency was 79.8%. As can be seen in fig. 12, at 1A g-1Under the high current density, the reversible specific capacity of the optimal sample EP-CYM-1400 is 70.6mA h g-1。
Application example 3
HM-1000, HM-1200, HM-1400 and HM-1600 in preparation example 6 were used as active materials to prepare negative electrodes of sodium ion batteries, and electrochemical charge and discharge performance tests were performed thereon, and the resulting batteries were named EP-HM-1000, EP-HM-1200, EP-HM-1400 and EP-HM-1600, respectively. The procedure and test method were the same as in application example 1.
The first constant current charge and discharge test results of the battery prepared in application example 3 described above are shown in fig. 13. As can be seen from fig. 13, at 0.02A g-1Compared with EP-HM-1000, EP-HM-1200 and EP-HM-1600, the EP-HM-1400 shows better electrochemical performance at the current density of (1). The specific first charge capacity of EP-HM-1400 is 338.8mA h g-1The first coulombic efficiency was 81.1%. The batteries prepared in the above application example 3 were in the ranges of 0.02, 0.05, 0.1, 0.2, 0.5A g-1The multiplying power performance test is carried out under the current density of (1), the charging and discharging voltage window is 0.01-3.00V, and the test result is shown in figure 15. As can be seen in FIG. 15, at 1A g-1Under the high current density, the reversible specific capacity of the optimal sample EP-HM-1400 is 76.0mA h g-1。
The first charge and discharge of the batteries prepared in the above application examples 1, 2 and 3 are as shown in fig. 7, 10 and 13. As can be seen in FIGS. 7, 10 and 13 below, EP-HM-1400 in application example 3 exhibited higher reversible specific capacity and first coulombic efficiency than EP-YM-1400 in application example 1 described above and EP-CYM-1400 in application example 2 described above.
As can be seen from FIGS. 7, 10 and 13, the capacity of the ramp region of EP-YM-1400, EP-CYM-1400 and EP-HM-1400 is set to 138.0mA h g-1Increased to 158.3mA hr g-1Thus, EP-HM-1400 has a higher capacity of the ramp region, making it possible to obtain a higher capacity. This is mainly due to the gradual decrease in the extent of deterioration of bituminous coal to sub-bituminous coal to lignite coal, aG/ADThe value is reduced from 0.44 of YM-1400 to 0.28 of HM-1400, the graphitization degree is reduced, the defects of the material are gradually increased, and more abundant adsorption active sites are provided.
In addition, the rate performance of the batteries prepared in the above application examples 1, 2, and 3 is shown in fig. 9, 12, and 15. As can be seen from fig. 9, 12 and 15, EP-HM-1400 prepared in application example 3 shows better rate capability than EP-YM-1400 prepared in application example 1 and EP-CYM-1400 prepared in application example 2, mainly because lignite has a small deterioration degree, a minimum graphitization degree, has more abundant defect active sites, shows a fast sodium adsorption and storage behavior, and thus EP-HM-1400 has a larger sodium storage capacity at a large current density.
The results of the elemental analysis and XPS analysis of the materials prepared in preparation examples 4, 5 and 6 are shown in table 3. It can be seen that HM-1400 has a higher proportion of sp than YM-14003Carbon shows that the lignite carbon generates more defect structures, has lower graphitization degree and is consistent with the result of Raman spectrum test. In addition, the oxygen-containing functional groups of HM-1400 and YM-1400 are mainly-OH and C ═ O, which provides abundant active sites for sodium storage of the material. Further research on element analysis of the samples YM-1400 and HM-1400 shows that HM-1400 has less carbon content than YM-1400 and contains more heteroatom defect structures, which is beneficial to rapid sodium adsorption and storage. In addition, the oxygen contents of HM-1400 and YM-1400 were 1.86 wt% and 1.54 wt%, respectively, indicating that HM-1400 had a higher oxygen content.
In addition, the first charge and discharge of the batteries prepared in the above application examples 1, 2, and 3 are shown in fig. 7, 10, and 13. It can be seen in FIGS. 7, 10 and 13 that the main reason for the high capacity of EP-HM-1400 compared to EP-YM-1400 and EP-CYM-1400 is due to the more gradual behavior between the high potential ramp region 0.5-1.0V. This part of the capacity is in combination with the oxygen-containing functional group and Na+This is consistent with the richer oxygen content of EP-HM-1400. Therefore, EP-HM-1400 can generate rapid sodium adsorption and storage reaction and still maintain high specific capacity under large current.
Application comparative example 1
YM-0-1400 in the preparation comparative example 4 was used as an active material for preparing a negative electrode of a sodium ion battery, and the electrochemical charge and discharge properties thereof were further tested, and the obtained battery was named EP-YM-0-1400. The procedure was as in application example 1.
The EP-YM-1400 prepared in application example 1 and the EP-YM-0-1400 prepared in comparative example 1 described above were each tested at 0.02A g-1Current densityThe following constant current charge/discharge curves show the results in fig. 8. As can be seen from the figure, the electrochemical performance of the bituminous coal-based hard carbon material can be obviously improved by deashing treatment, compared with the EP-YM-0-1400 in the application comparative example 1, the initial coulombic efficiency of the EP-YM-1400 in the application example 1 is improved to 80.0% from 76.5%, and the specific capacity is increased from 274.5mA h g-1Lifting to 317.5mA h g-1。
Comparative application example 2
CYM-0-1400 in preparation comparative example 6 was used as an active material for preparing a negative electrode of a sodium ion battery, and an electrochemical charge-discharge performance test was performed thereon, and the obtained battery was named EP-CYM-0-1400. The procedure was as in application example 1.
EP-CYM-1400 prepared as described above using example 2 and EP-CYM-0-1400 prepared using comparative example 2 were each tested at 0.02A g-1The charge-discharge curve at current density was constant, and the result is shown in fig. 11. As can be seen from the figure, compared with the EP-CYM-0-1400 in the application comparative example 2, the electrochemical performance of the EP-CYM-1400 in the application example is obviously improved, the coulombic efficiency is increased from 69.6 percent to 79.8 percent for the first time, and the specific capacity is increased from 193.2mA h g-1Lifting to 326.1mA h g-1。
Comparative application example 3
HM-0-1400 in preparation comparative example 8 was used as an active material for preparing a negative electrode of a sodium ion battery, and an electrochemical charge-discharge test was performed thereon, and the resulting battery was named EP-HM-0-1400. The procedure was as in application example 1.
The cell EP-HM-1400 prepared in the above application example 3 and the cell EP-HM-0-1400 prepared in the application comparative example 3 were each tested at 0.02A g-1The results of the constant current charge/discharge curve at the current density are shown in fig. 14 below. As can be seen from the graph, the electrochemical performance of EP-HM-0-1400 in the application comparative example 3 is remarkably advantageous as compared with that of EP-HM-1400 in the application example 3. The first coulombic efficiency is improved from 67.9 percent to 81.1 percent, and the specific capacity is improved from 137.1mA h g-1Lifting to 338.8mA h g-1。
The foregoing is considered as illustrative and not restrictive in character, and that various modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (19)
1. The coal-based hard carbon negative electrode material for the sodium ion battery is characterized in that the crystal face spacing d of the coal-based hard carbon material for the sodium ion battery002The value is more than 0.2 nm; preferably 0.2-0.5nm, more preferably 0.364-0.384 nm.
2. The sodium-ion battery coal-based hard carbon negative electrode material as claimed in claim 1, wherein A isG/ADThe value is 0.1 to 0.6, preferably 0.21 to 0.49.
3. The sodium ion battery coal-based hard carbon negative electrode material as claimed in any one of claims 1 to 2, wherein L is LcValues of 1 to 4nm, preferably 2.11 to 2.60 nm; l isaThe value is 0.5-2.5nm, preferably 1.75-2.18 nm.
4. The coal-based hard carbon negative electrode material of the sodium-ion battery as claimed in any one of claims 1 to 3, wherein the coal-based hard carbon negative electrode material is in a granular shape and has an average particle size of 28 to 470 μm.
5. The sodium-ion battery coal-based hard carbon negative electrode material is obtained by performing deashing treatment, carbonization treatment and programmed cooling treatment on raw material coal, wherein the raw material coal is one or more of bituminous coal, sub-bituminous coal and lignite, and is preferably lignite.
6. The coal-based hard carbon negative electrode material of the sodium-ion battery as claimed in claim 5, wherein the programmed cooling treatment is carried out at 1-5 ℃ for min-1Cooling to 15-30 deg.C.
7. The coal-based hard carbon negative electrode material of the sodium-ion battery as defined in claim 5 or 6, wherein the deashing treatment is 2-step deashing treatment with acid, preferably the 2-step deashing treatment is treatment with hydrochloric acid, hydrofluoric acid, nitric acid or sulfuric acid, wherein the acid used in the 2-step deashing treatment can be the same or different.
8. The method for preparing the coal-based hard carbon negative electrode material of the sodium-ion battery as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
step 1: crushing raw coal, sieving, treating in a deashing solution, washing with water to neutrality, and drying to obtain a carbon precursor;
step 2: and (3) carrying out high-temperature carbonization on the carbon precursor obtained in the step (1) under the protection of inert gas, and carrying out programmed cooling to 15-30 ℃ to obtain the coal-based hard carbon negative electrode material of the sodium ion battery.
9. The method for preparing the coal-based hard carbon negative electrode material of the sodium-ion battery according to claim 8, wherein in the step 1, the raw material coal is one or more of bituminous coal, sub-bituminous coal and lignite, and is preferably lignite.
10. The method for preparing the coal-based hard carbon negative electrode material of the sodium-ion battery according to claim 8, wherein in the step 1, the treatment in the deashing solution is 2-step deashing treatment by using acid; preferably, the 2-step deashing treatment is carried out by using hydrochloric acid, hydrofluoric acid, nitric acid or sulfuric acid, wherein the acids used in the 2-step deashing treatment can be the same or different.
11. The method for preparing the coal-based hard carbon negative electrode material of the sodium-ion battery as claimed in claim 8, wherein in the step 1, the dosage of the deashing solution is as follows: and (3) deashing the coal by using 10-30mL of acid per gram of coal.
12. The method for preparing the coal-based hard carbon negative electrode material of the sodium-ion battery as claimed in claim 8, wherein in the step 2, the inert gas used for carbonization is at least one of nitrogen and argon.
13. The method for preparing the coal-based hard carbon negative electrode material of the sodium-ion battery as claimed in claim 8, wherein in the step 2, the inert gas used for carbonization is introduced at a flow rate of 30-600cc min-1。
14. The method for preparing the coal-based hard carbon negative electrode material of the sodium-ion battery as claimed in claim 8, wherein in the step 2, the temperature is 1-5 ℃ for min-1The temperature is raised to 1000-1600 ℃ and kept for 1-4h, preferably 1-5 ℃ for min-1The temperature was raised to 1350-.
15. The method for preparing the coal-based hard carbon negative electrode material of the sodium-ion battery as claimed in claim 8, wherein in the step 2, the cooling process adopts program cooling at 1-5 ℃ for min-1Cooling to 15-30 deg.C.
16. A negative electrode plate of a sodium ion battery, characterized in that, the negative electrode plate includes: a conductive agent, a binder, a current collector, and the coal-based hard carbon material according to any one of claims 1 to 7.
17. The negative electrode plate of the sodium-ion battery as claimed in claim 16, wherein the binder on the negative electrode plate comprises one or more of sodium carboxymethylcellulose, sodium alginate, polyacrylic acid, PVD F, LA 133.
18. The negative electrode plate of the sodium-ion battery as claimed in claim 16, wherein the conductive agent on the negative electrode plate comprises one or more of carbon nanotubes, carbon fibers, graphene, acetylene black and Super P.
19. A sodium ion battery comprising the negative electrode tab of claim 16.
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