CN107240680B - hard carbon-metal oxide-soft carbon composite material and preparation method and application thereof - Google Patents
hard carbon-metal oxide-soft carbon composite material and preparation method and application thereof Download PDFInfo
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- CN107240680B CN107240680B CN201710361334.5A CN201710361334A CN107240680B CN 107240680 B CN107240680 B CN 107240680B CN 201710361334 A CN201710361334 A CN 201710361334A CN 107240680 B CN107240680 B CN 107240680B
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- 229910021384 soft carbon Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007833 carbon precursor Substances 0.000 claims abstract description 65
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000010426 asphalt Substances 0.000 claims abstract description 27
- 150000003608 titanium Chemical class 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 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
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 10
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 description 16
- 238000003763 carbonization Methods 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 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 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
the invention discloses a hard carbon-metal oxide-soft carbon composite material and a preparation method and application thereof.A hard carbon precursor is prepared by a hydro-thermal method of a hydrocarbon in a reaction kettle, then the hard carbon precursor and titanium salt are pre-coated, and asphalt is placed in a muffle furnace for low-temperature pyrolysis reaction to obtain a soft carbon precursor; and finally, fully mixing the pre-coated hard carbon precursor and the soft carbon precursor, and carrying out high-temperature pyrolysis reaction under the protection of inert gas to obtain a product, namely a hard carbon-metal oxide-soft carbon composite material, wherein the material can be used as a negative electrode active material of a sodium ion battery. The raw materials used by the invention have wide sources and low cost; the prepared hard carbon-metal oxide-soft carbon composite material has the advantages of large reversible capacity, high first charge-discharge coulombic efficiency, good cycle performance and the like in a sodium ion battery.
Description
Technical Field
The invention relates to a preparation method of a composite material, in particular to a hard carbon-metal oxide-soft carbon composite material and a preparation method and application thereof.
Background
Compared with traditional secondary batteries such as lead-acid batteries and nickel-cadmium batteries, the lithium ion battery has the advantages of high working voltage, high energy density, long cycle life, environmental friendliness and the like, thereby attracting more and more attention of scientific researchers. However, the global lithium resource is not abundant, the abundance of lithium element in earth crust is only 0.006%, the resource and price problems become a concern for future large-scale application, and the development of a new energy storage battery system with excellent comprehensive performance is urgently needed. Compared with lithium resources, the sodium reserves are very rich, the content in the earth crust is about 2.64 percent, the sodium reserves and the earth crust are the same main group elements, the chemical properties are similar, and the development of the sodium ion battery by using sodium to replace lithium has very wide application prospects.
At present, the cathode materials commonly used in lithium ion batteries are natural graphite, artificial graphite and the like, which have excellent cycle performance, but sodium ions with relatively large radius are difficult to be embedded into the graphite interlayer spacing, so that the development of novel cathode materials for sodium ion batteries has become a focus of research.
hard carbon is pyrolytic carbon of high molecular polymer, which is difficult to graphitize, and has layers which are staggered with each otherThe structure enables sodium ions to be embedded and extracted from various angles, thereby greatly improving the charging and discharging speed; compared with graphite materials, the low-temperature performance of the composite material is also obviously improved, and the hard carbon material generally has higher reversible specific capacity, but the hard carbon material also has the defects of overhigh electrode potential, potential hysteresis, primary irreversibility, large capacity and the like, so that the large-scale application of the composite material is limited. The soft carbon material refers to amorphous carbon capable of being graphitized at a high temperature of 2500 ℃ or more, and has a smaller specific surface area and better electrolyte compatibility than the hard carbon material. Compared with the carbon materials currently used, TiO2the sodium ion battery has the advantages of high dielectric constant, good chemical stability and thermal stability and the like, so that the sodium ion battery has the advantages of small initial irreversible capacity loss, good safety performance and the like. Therefore, the hard carbon material is used as the core, the hard carbon-metal oxide-soft carbon composite material is prepared by double-layer coating of the metal oxide and the soft carbon material, and the lithium ion battery using the composite material as the active material has the advantages of high reversible capacity, good cycle performance, high safety performance and the like, and meanwhile, the preparation method is simple and the cost is low.
Disclosure of Invention
The invention aims to provide a sodium ion battery cathode material with low price, good cycle performance and high capacity and a preparation method thereof.
the invention is realized by the following scheme:
A method for preparing a hard carbon-metal oxide-soft carbon composite material, comprising the steps of:
1) putting a hydrocarbon aqueous solution into a reaction kettle for hydrothermal reaction, then washing with water until the pH value is neutral, and drying to obtain a hard carbon precursor;
2) Adding a hard carbon precursor and a titanium salt into a mixed solution of a solvent and deionized water, stirring, and drying after the titanium salt is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
3) putting the asphalt into a muffle furnace for low-temperature pyrolysis reaction to decompose light components in the asphalt to obtain a soft carbon precursor;
4) and uniformly mixing the pre-coated hard carbon precursor and the soft carbon precursor, and carrying out high-temperature pyrolysis reaction under the protection of inert gas to obtain the hard carbon-metal oxide-soft carbon composite material.
in a further scheme, the hydrocarbon in the step 1) is at least one of glucose, sucrose, lignin and cellulose; the temperature of the hydrothermal reaction is 100-300 ℃.
in a further scheme, the titanium salt in the step 2) is butyl titanate or titanium isopropoxide; the solvent is one of ethanol, ethylene glycol and propylene glycol, the volume ratio of the solvent to the deionized water is 3:7, and the solvent mainly plays a role of a dispersing agent.
In a further scheme, the asphalt in the step 3) is at least one of coal tar asphalt, mesophase asphalt and petroleum asphalt; the temperature of the low-temperature pyrolysis reaction is 25-400 ℃, and the time is 12-48 h.
In a further scheme, the mass ratio of the hard carbon precursor, the titanium salt and the soft carbon precursor in the hard carbon-metal oxide-soft carbon composite material is (60-100): (5-20): (5-20).
Further, the inert gas in the step 4) is nitrogen, argon or helium.
In a further scheme, the temperature of the high-temperature pyrolysis reaction in the step 4) is 700-1200 ℃, and the time is 2-6 hours.
The second object of the present invention is to provide a hard carbon-metal oxide-soft carbon composite material prepared by the above preparation method.
A third object of the present invention is to provide use of a hard carbon-metal oxide-soft carbon composite for a negative active material of a sodium ion secondary battery.
the hard carbon-metal oxide-soft carbon composite material is synthesized by a thermal decomposition method, the inner core is made of hard carbon material, the specific capacity is higher, the interlayer spacing is larger than that of graphite, and the diffusion speed of lithium ions in the hard carbon material is higher, so that the low-temperature performance and the rate capability of the battery can be improved. The coating layer of the composite material is a double-layer coating of the metal oxide and the soft carbon material, the metal oxide coating layer can reduce the first irreversible capacity of the hard carbon material, and the structural stability of the metal oxide coating layer ensures the safety of the negative electrode material; the soft carbon material has smaller specific surface area and good conductivity, on one hand, the reversible capacity of the composite material is improved, on the other hand, the soft carbon material is beneficial to reacting with the electrolyte to generate a stable and compact SEI film, and the better cycle performance and the higher charge-discharge efficiency of the battery are ensured.
The raw materials used by the invention have wide sources and low cost; the hard carbon-metal oxide-soft carbon composite material prepared by the invention has the advantages of large reversible capacity, high first charge-discharge coulombic efficiency, good cycle performance and the like in a sodium ion battery.
Detailed Description
in order to further understand the contents and features of the present invention, the following examples are given, but these examples do not limit the whole contents of the idea of the present invention.
Example 1
1) Adding a 0.5M glucose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 180 ℃, and controlling the hydrothermal reaction time to be 8 h;
2) Washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and tetrabutyl titanate into an ethanol-water solution (the volume ratio of ethanol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the tetrabutyl titanate is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
5) and (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 60:20:20, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 800 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Example 2
1) adding a 0.5M glucose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 100 ℃, and controlling the hydrothermal reaction time to be 16 h;
2) Washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and titanium isopropoxide into an ethylene glycol-water solution (the volume ratio of ethylene glycol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after titanium isopropoxide is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
5) And (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 60:20:20, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 900 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Example 3
1) Adding a sucrose aqueous solution with the concentration of 0.6M into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 180 ℃, and performing hydrothermal reaction for 10 hours;
2) Washing the reactant obtained in the step 1) with deionized water, performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding a hard carbon precursor and tetrabutyl titanate into a propylene glycol-water solution (the volume ratio of propylene glycol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the tetrabutyl titanate is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) Putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
5) And (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 80:10:10, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 900 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Example 4
1) Adding a lignin aqueous solution with the concentration of 0.4M into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 240 ℃, and performing hydrothermal reaction for 10 hours;
2) washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and tetrabutyl titanate into an ethanol-water solution (the volume ratio of ethanol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the tetrabutyl titanate is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
5) And (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 80:10:10, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 900 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Example 5
1) Adding a 0.6M cellulose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 200 ℃, and controlling the hydrothermal reaction time to be 8 hours;
2) washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and tetrabutyl titanate into an ethanol-water solution (the volume ratio of ethanol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the tetrabutyl titanate is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 380 ℃ for 12h, and obtaining a soft carbon precursor after decomposing light components in the asphalt;
5) and (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 90:5:5, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 1200 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
example 6
1) Adding a 0.6M cellulose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 300 ℃, and controlling the hydrothermal reaction time to be 6 h;
2) washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) Adding the hard carbon precursor and titanium isopropoxide into an ethanol-water solution (the volume ratio of ethanol to deionized water is 3:7), stirring for 4 hours, and filtering and drying after the titanium isopropoxide is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
4) Putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 380 ℃ for 22h, and obtaining a soft carbon precursor after decomposing light components in the asphalt;
5) and (3) fully mixing the two precursor products obtained in the steps 3) and 4) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is 90:5:5, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 1200 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-metal oxide-soft carbon composite material.
Comparative example 1
1) adding a 0.5M glucose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 180 ℃, and controlling the hydrothermal reaction time to be 8 h;
2) Washing the reactant obtained in the step 1) with deionized water, and performing suction filtration for 3 times until the pH value is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor material;
3) putting the crucible filled with the asphalt into a muffle furnace, pyrolyzing the crucible at 220 ℃ for 22h, and obtaining a soft carbon precursor after light components in the asphalt are decomposed;
4) And (3) fully mixing the two precursor products obtained in the steps 2) and 3) through a planetary ball mill, wherein the mass ratio of the hard carbon precursor to the soft carbon precursor is 90:10, and carrying out high-temperature carbonization reaction on the mixture under the protection of inert gas, wherein the carbonization temperature is 800 ℃ and the reaction time is 4h, so as to finally obtain the hard carbon-soft carbon composite material.
comparative example 2
1) adding a 0.5M glucose aqueous solution into a reaction kettle, then placing the reaction kettle into an oven, controlling the temperature of the oven at 180 ℃, and controlling the hydrothermal reaction time to be 8 h;
2) and (2) carrying out high-temperature carbonization reaction on the hard carbon precursor product obtained in the step 1) under the protection of inert gas, wherein the carbonization temperature is 800 ℃, and the reaction time is 4h, so as to finally obtain the hard carbon material.
the materials prepared in the above examples 1 to 6 and comparative examples 1 to 2 were used as negative electrode active materials of sodium ion batteries, and were subjected to normal-temperature charge-discharge and cycle performance tests: mixing a hard carbon material, a conductive agent and a binder according to a mass ratio of 8:1:1 to prepare a pole piece, taking metal sodium as a counter electrode, and taking 1mol/L of NaFP as electrolyte6EC: DMC 1: 1(w: w) and the separator used was PP (Celgard 2400), the button cells were assembled in an argon atmosphere glove box and the button cells were tested for charging and discharging in the voltage range 0.001-2.0V (vs. Na)+Na) with a current density of 50mA g-1. The results of the performance tests of each cell are shown in table 1 below (the data results are averaged after 3 tests were performed).
Table 1: performance testing
note: the battery is subjected to constant current charge and discharge at a cycle test temperature of 25 ℃ and a current density of 50 mA/g.
as can be seen from the above table 1, the composite material of the present invention is a double-layer clad structure of metal oxide and soft carbon, which reduces the first discharge capacity, but improves the first coulombic efficiency and capacity retention rate of the composite material; on the other hand, excessive metal oxide coating may also result in lower electrical conductivity of the composite, thereby reducing the cycle performance of the composite. According to the invention, the ratio of the hard carbon precursor, the titanium salt and the soft carbon precursor is regulated, so that the prepared hard carbon-metal oxide-soft carbon composite material can effectively improve the first coulombic efficiency and the capacity retention rate of the battery.
the hard carbon precursor material prepared in the comparative example 1 is not pre-coated with titanium salt, so that the first coulombic efficiency and the capacity retention rate are poor; the hard carbon material prepared in comparative example 2 has a higher first capacity because it is not coated, but a larger specific surface area causes a higher first irreversible capacity, thereby reducing the first coulombic efficiency and poor cycle stability.
Having thus described in detail preferred embodiments of the present invention, it will be apparent to those skilled in the art that many variations, modifications, and alterations to these embodiments may be practiced based on the teachings of the present invention, which are intended to be covered by the appended claims.
Claims (8)
1. a preparation method of a hard carbon-metal oxide-soft carbon composite material is characterized by comprising the following steps: the method comprises the following steps:
1) Putting a hydrocarbon aqueous solution into a reaction kettle for hydrothermal reaction, then washing with water until the pH is neutral, and drying at 80-120 ℃ for more than or equal to 24 hours to obtain a hard carbon precursor;
2) Adding the hard carbon precursor and titanium salt into a mixed solvent containing deionized water, stirring, and drying after the titanium salt is fully hydrolyzed to obtain a pre-coated hard carbon precursor;
3) Placing the asphalt in a muffle furnace for low-temperature pyrolysis reaction to decompose light components in the asphalt to obtain a soft carbon precursor, wherein the temperature of the low-temperature pyrolysis reaction is 220-400 ℃;
4) Uniformly mixing the pre-coated hard carbon precursor and the soft carbon precursor, and carrying out high-temperature pyrolysis reaction under the protection of inert gas, wherein the temperature of the high-temperature pyrolysis reaction is 700-1200 ℃, so as to obtain a hard carbon-metal oxide-soft carbon composite material; the mass ratio of the hard carbon precursor to the titanium salt to the soft carbon precursor is (60-100): (5-20): (5-20).
2. The method of claim 1, wherein: the hydrocarbon in the step 1) is at least one of glucose, sucrose, lignin and cellulose; the temperature of the hydrothermal reaction is 100-300 ℃.
3. the method of claim 1, wherein: the titanium salt in the step 2) is butyl titanate or titanium isopropoxide; the mixed solvent is formed by mixing deionized water and ethanol or by mixing deionized water and propylene glycol; the volume ratio of the ethanol to the deionized water in the mixed solvent is 3:7, or the volume ratio of the propylene glycol to the deionized water in the mixed solvent is 3: 7.
4. the method of claim 1, wherein: the asphalt in the step 3) is at least one of coal tar asphalt, mesophase asphalt and petroleum asphalt; the time of the low-temperature pyrolysis reaction is 12-48 h.
5. The method of claim 1, wherein: the inert gas in the step 4) is nitrogen, argon or helium.
6. the method of claim 1, wherein: the time of the high-temperature pyrolysis reaction in the step 4) is 2-6 h.
7. A hard carbon-metal oxide-soft carbon composite material prepared by the preparation method of claim 1.
8. Use of the hard carbon-metal oxide-soft carbon composite according to claim 7, wherein: the hard carbon-metal oxide-soft carbon composite material is used as a negative active material of a sodium ion secondary battery.
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| CN108878805B (en) * | 2018-05-30 | 2022-07-15 | 宁波柔创纳米科技有限公司 | Hard carbon negative electrode material, preparation method thereof, negative electrode plate and battery |
| CN109980212A (en) * | 2019-04-24 | 2019-07-05 | 陕西科技大学 | A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method |
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| CN114420938B (en) * | 2022-03-31 | 2022-06-21 | 河北坤天新能源股份有限公司 | Metal oxide amorphous carbon coated hard carbon composite material and preparation method and application thereof |
| CN114843483B (en) * | 2022-05-23 | 2024-05-07 | 常州烯源谷新材料科技有限公司 | Hard carbon composite material and preparation method and application thereof |
| CN115020674A (en) * | 2022-07-05 | 2022-09-06 | 晖阳(贵州)新能源材料有限公司 | Preparation method of cobalt oxide coated hard carbon composite negative electrode material |
| CN115520851B (en) * | 2022-09-30 | 2023-08-15 | 深圳市金牌新能源科技有限责任公司 | Preparation method of hard carbon-soft carbon-fast ion conductor composite material |
| CN115744872B (en) * | 2022-12-16 | 2024-01-09 | 天津理工大学 | Asphalt-based soft carbon composite cellulose hard carbon negative electrode material and preparation method thereof |
| CN115893405A (en) * | 2023-02-10 | 2023-04-04 | 珠海科创能源技术有限公司 | Method for manufacturing hard carbon of negative electrode of sodium ion battery |
| CN116675213B (en) * | 2023-05-30 | 2024-02-23 | 洛阳师范学院 | Carbon material and preparation method and application thereof |
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