WO2023160017A1 - 植物绒球硬碳复合负极材料及其制备方法和应用 - Google Patents
植物绒球硬碳复合负极材料及其制备方法和应用 Download PDFInfo
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- negative electrode
- electrode material
- hard carbon
- carbon composite
- composite negative
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 51
- 241001388119 Anisotremus surinamensis Species 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 39
- 238000005245 sintering Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 241000196324 Embryophyta Species 0.000 claims description 17
- 239000000017 hydrogel Substances 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- YVWPNDBYAAEZBF-UHFFFAOYSA-N trimethylsilylmethanamine Chemical group C[Si](C)(C)CN YVWPNDBYAAEZBF-UHFFFAOYSA-N 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 10
- 229910010093 LiAlO Inorganic materials 0.000 claims description 9
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 9
- 229910012404 LiSnO Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 240000003870 Ageratum houstonianum Species 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 240000001949 Taraxacum officinale Species 0.000 claims description 3
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 229910007562 Li2SiO3 Inorganic materials 0.000 abstract 1
- 229910010092 LiAlO2 Inorganic materials 0.000 abstract 1
- 229910012420 LiSnO2 Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 9
- 238000010008 shearing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 206010061592 cardiac fibrillation Diseases 0.000 description 6
- 230000002600 fibrillogenic effect Effects 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910017090 AlO 2 Inorganic materials 0.000 description 2
- 244000223760 Cinnamomum zeylanicum Species 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 235000017803 cinnamon Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 244000303040 Glycyrrhiza glabra Species 0.000 description 1
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- -1 Lithium hexafluorophosphate Chemical compound 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- QQGWBRJQPRTJDA-UHFFFAOYSA-N [Li].CC(O)=O Chemical compound [Li].CC(O)=O QQGWBRJQPRTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000011477 liquorice Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
Definitions
- the invention belongs to the technical field of battery materials, and in particular relates to a plant pompon hard carbon composite negative electrode material and a preparation method and application thereof.
- Lithium-ion batteries have attracted extensive attention due to their high energy density, long service life, and good environmental compatibility.
- lithium battery materials with higher voltage, higher energy density and superior rate performance are required, while improving cost, cycle life and safety.
- Hard carbon obtained from plant sources such as sugarcane stalks, cotton, pine nut husks, peanut husks, and rice husks, is an abundant and low-cost raw material, which has also attracted people's attention as a precursor of hard carbon.
- the development of potential hard carbon precursors is conducive to promoting the exploration of environmentally friendly and low-cost lithium-ion battery anode materials for large-scale production.
- Hard carbon materials are widely used in the fields of energy storage and conversion, but traditional hard carbon composite anode materials have low theoretical capacity and energy density, few active sites, and low reversible capacity, which limits their application in lithium-ion batteries, super Applications in capacitors and electrocatalysis.
- the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a kind of plant fluffy hard carbon composite negative electrode material and its preparation method and application. Specific surface area and conductivity of composite anode materials.
- the present invention adopts the following technical solutions:
- a hard carbon composite negative electrode material comprising the following raw materials: plant fluff, oxidant, lithium source, dispersant, and carboxyl-containing lithium salt; the lithium source is at least one of LiAlO 2 , Li 2 SiO 3 , and LiSnO 2 .
- the dispersant is one of aminomethyltrimethylsilane solution and N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane.
- the dispersant is an aminomethyltrimethylsilane solution.
- the oxidizing agent is LiClO.
- the plant pompon is at least one of liquorice grass, dandelion, cinnamon, and ageratum.
- the carboxyl-containing lithium salt is lithium acetate.
- the specific surface area of the hard carbon composite negative electrode material is 10-15 m 2 /g.
- the specific surface area of the hard carbon composite negative electrode material is 11-14 m 2 /g.
- the delithiation specific capacity of the hard carbon composite negative electrode material is 330.5-340mAh g -1 ; the first effect is 71-76%.
- a preparation method for a hard carbon composite negative electrode material comprising the following steps:
- the plant pompon is at least one of liquor grass, dandelion, cinnamon or ageratum.
- drying the plant fluff balls is also included, and the drying temperature is 80° C.-100° C.; the drying atmosphere is a nitrogen atmosphere.
- the dispersant is one of aminomethyltrimethylsilane solution and N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane.
- the dispersant is an aminomethyltrimethylsilane solution.
- the mass concentration of the aminomethyltrimethylsilane solution is 0.001-0.2 wt%.
- the solid-to-liquid ratio of the plant fluff balls and the dispersant is (1-10) g: 100 mL.
- the specific step of the homogeneous treatment is: performing shearing treatment on the homogeneous fluff liquid obtained after mixing the plant fluff and the dispersant to obtain a homogeneous fluff liquid.
- the gap between the shearing grooves is ⁇ 50 ⁇ m, and the shearing time is controlled within 5-30 minutes.
- the diameter of the filaments in the homogeneous pompom filament liquid is ⁇ 10 ⁇ m.
- the oxidizing agent is LiClO.
- the amount of LiClO added is 0.5-3 wt% of the pompom filaments.
- the lithium source is at least one of LiAlO 2 , Li 2 SiO 3 , and LiSnO 2 .
- the lye is LiOH solution.
- the pH of the lithium alkali oxidation treatment is 9-14
- the time of the lithium alkali oxidation treatment is 2-6 hours
- the temperature of the lithium alkali oxidation treatment is room temperature.
- the Li content of the lithium alkali oxidation treatment is 0.0001-0.08 mol/L.
- the carboxyl-containing lithium salt is lithium acetate.
- the drying temperature is 60-90° C.
- the drying time is 4-12 hours.
- the temperature of the primary sintering is 400-500° C., and the time of the primary sintering is 2-6 hours.
- the atmosphere for the primary sintering is one of argon, nitrogen and neon.
- the temperature of the secondary sintering is 500-1200° C., and the time of the secondary sintering is 2-6 hours.
- the atmosphere of the secondary sintering is one of argon, nitrogen and neon.
- the gas flow rate of the secondary sintering is 10-50 mL/min.
- the length of the hard carbon composite negative electrode material is ⁇ 20 ⁇ m.
- the present invention also provides the application of the above-mentioned hard carbon composite negative electrode material in preparing batteries, catalysts and supercapacitors.
- the present invention first mixes the dispersing agent and the plant pompon, because the dispersing agent contains aminomethyltrimethylsilane, which can help the pompon to disperse evenly in the solution, and the silyl groups on the aminomethyltrimethylsilane
- the silane group can gradually replace the hydroxyl group on the surface of the pompom under stirring.
- the silane group is reactive to inorganic ions and has better binding performance to inorganic ions, so it can strengthen the ability to subsequently adsorb metal ions; then add oxidant, lithium source and alkali
- the solution is subjected to lithium alkali oxidation treatment, and the various functional groups of the pompom filaments are gradually exposed under the oxidation of the oxidizing agent.
- the multi-group cross-linking reaction with the hydroxyl group can be further exposed. More functional groups, so Reciprocating, the oxygen-containing active sites increase, which is conducive to the grafting reaction of the fluffy filaments of the loosened cross-linked network, so that the fluffy filaments adsorb more AlO 2 - , and finally the specific capacity of the hard carbon composite negative electrode material is increased by sintering. And the first effect is improved, and the electrochemical performance is greatly improved.
- the lithium source contains LiAlO 2 , after sintering, the pompom filaments adsorb more AlO 2 - , which can improve the hardness of the hard carbon composite negative electrode material.
- the lithium source also contains Li 2 SiO 3 , LiSnO 2 , after sintering, the pompon filaments adsorb, SiO 3 2+ /SnO 2 - , and the theoretical capacity of Si/Sn is higher than that of hard carbon High, through the reasonable combination of Si/Sn and pompom hard carbon, thus improving the energy density of pompom hard carbon composite anode materials.
- Fig. 1 is the SEM picture of the hard carbon composite negative electrode material that the embodiment of the present invention 1 makes;
- FIG. 2 is an XRD pattern of the hard carbon composite negative electrode material prepared in Example 1 of the present invention.
- Fig. 1 is the SEM picture of the hard carbon composite negative electrode material that the embodiment of the present invention 1 makes; As can be seen from Fig. 1, the diameter of the pompom filament is between 0.1-4 micron, and the diameter concentration of the material is better, and the shape of the material is better. The consistency is better.
- Fig. 2 is the XRD pattern of the hard carbon composite negative electrode material that the present invention embodiment 1 makes; As can be seen from Fig. 2, the prepared material has two diffraction peaks to exist, and the interlayer distance is larger, shows that the prepared material is composite Material.
- Comparative example 1 (do not add lye to carry out lithium alkali oxidation treatment)
- the preparation method of the hard carbon composite negative electrode material of this comparative example comprises the following steps:
- Comparative example 2 (dispersant is ethanol solution)
- the preparation method of the hard carbon composite negative electrode material of this comparative example comprises the following steps:
- the hard carbon composite negative electrode material, acetylene black and polyvinylidene fluoride prepared in Examples 1-4 and Comparative Example 1-2 were dissolved in N-methylpyrrolidone according to the mass ratio of 8:1:1, and ground Form a paste-like active material, then apply the paste-like active material evenly on the Cu foil substrate, put it in a vacuum oven, and dry it at 85°C for 8h to make an electrode sheet, use the lithium sheet as the counter electrode, and the electrolyte is 1mol/ L Lithium hexafluorophosphate (LiPF6) EC/DMC/DEC (mixed solution with a mass ratio of 1:1:1), assembled into a CR2025 button cell in a glove box, on a LAND battery test system, at 0.1A/g Current density, electrochemical energy test was performed at 0.01-3V.
- LiPF6 Lithium hexafluorophosphate
- Table 1 is a comparison of the specific surface area of the samples prepared in Examples 1, 2, 3, 4 and Comparative Examples 1 and 2, and it is found that the specific surface area of the samples of the Examples is higher than that of the Comparative Examples.
- Table 2 is a comparison of the electrochemical properties of the samples prepared in Examples 1, 2, 3, 4 and Comparative Examples 1, 2. It is found from the examples that as the nitrogen flow increases in the sintering process, the specific capacity of the prepared material and the first effect are all increased, and the specific capacity and the first effect of the embodiment prepared by the method of the present invention are higher than that of the comparative example.
- Example 1 330.5 71.75
- Example 2 332.8 73.19
- Example 3 340.7 75.29
- Example 4 331.6 72.19 Comparative example 1 300.1 50.12 Comparative example 2 308.2 61.69
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Abstract
一种植物绒球硬碳复合负极材料及其制备方法和应用,制备硬碳复合负极材料的原料包括:植物绒球、氧化剂、锂源、分散剂和含羧基的锂盐;锂源为LiAlO 2、Li 2SiO 3、LiSnO 2中的至少一种。硬碳复合负极材料的三维微米结构中具有丰富的孔隙,提高了硬碳复合负极材料的比表面积和导电性;在硬碳复合负极材料的碳中引入N、O等杂原子材料还可以提高其电化学性能,由于N原子和C原子具有相似的电子排列方式,使得碳骨架中的C元素更容易被N原子取代,从而改变碳材料的表面官能团以提高其电化学性能,即提高了硬碳复合负极材料的比容量和首效。
Description
本发明属于电池材料技术领域,具体涉及植物绒球硬碳复合负极材料及其制备方法和应用。
锂离子电池(LIBs)因其能量密度高、使用寿命长、环境兼容性良好等优点而受到广泛关注。然而随着携式电子产品、电动汽车和可再生发电站等的大规模发展,需要更高的电压、更高的能量密度和优越的速率性能锂电池材料,同时提高了成本、循环寿命和安全。为了能够缓解矿产资源发掘的压力,拥有和石墨类似能储锂的硬碳电极材料引起人们的关注。从植物来源获得的硬碳,如甘蔗秆,棉花,松果壳,花生壳和稻壳等其丰富且成本低廉原材料,作为硬碳的前体也引起了人们的关注,有来源广泛、产量巨大、制备绿色、可再生、机械性能优异和改性位点多等显著优点。开发潜力的硬碳的前体,有利于推动探索环境友好、成本低廉的锂离子电池负极材料的大规模生产。
硬碳材料在能源储存与转化等领域具有广泛应用,但传统的硬碳复合负极材料理论容量和能量密度低、活性位点少,此外可逆容量较低等,限制了其在锂离子电池、超级电容器以及电催化方面的应用。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种植物绒球硬碳复合负极材料及其制备方法和应用,制备的植物绒球硬碳复合负极材料的三维微米结构中具有丰富的孔隙,提高了植物绒球硬碳复合负极材料的比表面积和导电性。
为实现上述目的,本发明采用以下技术方案:
一种硬碳复合负极材料,包括以下原料:植物绒球、氧化剂、锂源、分散剂和含羧基的锂盐;所述锂源为LiAlO
2、Li
2SiO
3、LiSnO
2中的至少一种。
优选地,所述分散剂为氨甲基三甲基硅烷溶液、N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷中的一种。
进一步优选地,所述分散剂为氨甲基三甲基硅烷溶液。
优选地,所述氧化剂为LiClO。
优选地,所述植物绒球为白酒草、蒲公英、朱缨花、藿香蓟中的至少一种。
优选地,所述含羧基的锂盐为醋酸锂。
优选地,所述硬碳复合负极材料的比表面积为10-15m
2/g。
进一步优选地,所述硬碳复合负极材料的比表面积为11-14m
2/g。
优选地,所述硬碳复合负极材料的脱锂比容量为330.5-340mAh g
-1;首效为71-76%。
一种硬碳复合负极材料的制备方法,包括以下步骤:
(1)将植物绒球和分散剂混合,再进行均质处理,得到均质绒球细丝液;
(2)将所述均质绒球细丝液、氧化剂、锂源和碱液混合,进行锂碱氧化处理,再加入含羧基的锂盐,进行接枝反应,搅拌分层,分离,取上层悬浮物质,得到绒球细丝水凝胶;
(3)将所述绒球细丝水凝胶进行干燥,进行一次烧结,升温,进行二次烧结,得到硬碳复合负极材料。
优选地,步骤(1)中,所述植物绒球为白酒草、蒲公英、朱缨花或藿香蓟中的至少一种。
优选地,步骤(1)中,所述植物绒球和分散剂混合前还包括将植物绒球进行干燥处理,所述干燥的温度为80℃-100℃;干燥的气氛为氮气气氛。
优选地,步骤(1)中,所述分散剂为氨甲基三甲基硅烷溶液、N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷中的一种。
进一步优选地,所述分散剂为氨甲基三甲基硅烷溶液。
进一步优选地,所述氨甲基三甲基硅烷溶液的质量浓度为0.001-0.2wt%。
优选地,步骤(1)中,所述植物绒球和分散剂的固液比为(1-10)g:100mL。
优选地,步骤(1)中,所述均质处理的具体步骤为:将植物绒球和分散剂混合后得到的均质绒球液进行剪切处理,得到均质绒球细丝液。
进一步优选地,所述剪切槽的间隙<50μm,剪切的时间控制在5-30min。
优选地,步骤(1)中,所述均质绒球细丝液中的细丝直径<10μm。
优选地,步骤(2)中,所述氧化剂为LiClO。
进一步优选地,所述LiClO加入量为质绒球细丝的0.5-3wt%。
优选地,步骤(2)中,所述锂源为LiAlO
2、Li
2SiO
3、LiSnO
2中的至少一种。
优选地,步骤(2)中,所述碱液为LiOH溶液。
优选地,步骤(2)中,所述锂碱氧化处理的pH为9-14,锂碱氧化处理的时间为2-6h,锂碱氧化处理的温度为室温。
优选地,步骤(2)中,所述锂碱氧化处理的Li含量在0.0001-0.08mol/L。
优选地,步骤(2)中,所述含羧基的锂盐为醋酸锂。
优选地,步骤(3)中,所述干燥的温度为60-90℃,干燥的时间为4-12h。
优选地,步骤(3)中,所述一次烧结的温度为400~500℃,一次烧结的时间为2~6h。
优选地,步骤(3)中,所述一次烧结的气氛为氩气、氮气、氖气中的一种。
优选地,步骤(3)中,所述二次烧结的温度为500-1200℃,二次烧结的时间为2~6h。
优选地,步骤(3)中,所述二次烧结的气氛为氩气、氮气、氖气中的一种。
优选地,步骤(3)中,所述二次烧结的气流量为10-50mL/min。
优选地,步骤(3)中,所述硬碳复合负极材料的长度<20μm。
本发明还提供上述硬碳复合负极材料在制备电池、催化剂、超级电容器中的应用。
相对于现有技术,本发明的有益效果如下:
(1)本发明制备的硬碳复合负极材料的三维微米结构中具有丰富的孔隙,提高了硬碳复合负极材料的比表面积;在硬碳复合负极材料的碳中引入N、O等杂原子材料还可以提高其电化学性能,由于N原子和C原子具有相似的电子排列方式,使得碳骨架中的C元素更容易被N原子取代,从而改变碳材料的表面官能团以提高其电化学性能,即提高了硬碳复合负极材料的比容量和首效提升。
(2)本发明先将分散剂和植物绒球混合,由于分散剂中含氨甲基三甲基硅烷,可帮助绒球均匀分散在溶液中,此外氨甲基三甲基硅烷上的硅烷基团可在搅拌下逐渐取代绒球表面的羟基,硅烷基团对无机离子具有反应性,对无机离子结合性能更佳,因此可强化对后续吸附金属离子的能力;再加入氧化剂、锂源和碱液进行锂碱氧化处理,在氧化剂的氧化下逐渐将绒球细丝的各种官能团暴露出来,加碱后与羟基基团进行多基团的交联反应,又能进一步暴露更多官能团,如此往复,含氧活性位点增加,利于后面松散化的交联网络的绒球细丝接枝反应,使得绒球细丝吸附较多AlO
2
-,最后通过烧结使得硬碳复合负极材料的比容量和首效提升,电化学性能得到大幅度提高。
(3)本发明加入锂源和碱液进行锂碱氧化处理的过程中,由于锂源中含有LiAlO
2,经过烧结后,绒球细丝吸附较多AlO
2
-,能提高硬碳复合负极材料的比容量和首效,锂源中还含有Li
2SiO
3、LiSnO
2,经过烧结后,绒球细丝吸附,SiO
3
2+/SnO
2
-,而Si/Sn的理论容量较硬碳的高,通过Si/Sn与绒球硬碳合理结合,因此提高绒球硬碳复合负极材料的能量密度。
图1为本发明实施例1制得的硬碳复合负极材料的SEM图;
图2为本发明实施例1制得的硬碳复合负极材料的XRD图。
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
本实施例的硬碳复合负极材料的制备方法,包括以下步骤:
(1)将植物绒球(pompon)置于氮气气氛下85℃干燥处理3.5h,将干燥后的绒球、0.023wt%氨甲基三甲基硅烷溶液按固液比为1.2g:100mL混合,得到均质绒球液,将均质绒球液进行剪切细丝化处理6次(每次处理时间为16min),得到均质绒球细丝液(细丝直径<10μm)。
(2)将均质绒球细丝液与LiClO(LiClO加入量为均质绒球细丝的0.71wt%)进行混合,并加LiAlO
2+LiOH混合物(其中,Li含量在0.027mol/L)进行锂碱氧化处理3.5h(pH为10.3),得到氧化后的均质绒球细丝液,将氧化后的均质绒球细丝液送至搅拌器,将0.35g醋酸锂加入搅拌器中,搅拌,分层,分离,取上层悬浮物质,得到绒球细丝水凝胶。
(3)将绒球细丝水凝胶在65℃下进行真空干燥6.5h,得到绒球细丝,然后置于氮气气氛下(流量为12mL/min),先在462℃下进行一次烧结3h,再升高温度至823℃进行二次烧结3.6h,降温、洗涤、干燥、超声粉碎,得到硬碳复合负极材料。
图1为本发明实施例1制得的硬碳复合负极材料的SEM图;从图1中可知,绒球细丝直径在0.1-4微米之间,材料直径集中度较好,材料形貌的一致性较佳。
图2为本发明实施例1制得的硬碳复合负极材料的XRD图;从图2中可知,所制备的材料有两个衍射峰存在,且层间距较大,表明所制备的材料为复合材料。
实施例2
本实施例的硬碳复合负极材料的制备方法,包括以下步骤:
(1)将植物绒球(pompon)置于氮气气氛下85℃干燥处理3.5h,将干燥后的绒球、0.0654wt%氨甲基三甲基硅烷溶液按固液比为2.8g:100mL混合,得到均质绒球液,将均质绒球液进行剪切细丝化处理6次(每次处理时间为16min),得到均质绒球细丝液(细丝直径<10μm)。
(2)将均质绒球细丝液与LiClO(LiClO加入量为均质绒球细丝的0.86wt%)进行混合,并加LiAlO
2+Li
2SiO
3+LiOH混合物(其中,Li含量在0.036mol/L)进行锂碱氧化处理3.5h(pH 为10.3),得到氧化后的均质绒球细丝液,将氧化后的均质绒球细丝液送至搅拌器,将0.35g醋酸锂加入搅拌器中,搅拌,分层,分离,取上层悬浮物质,得到绒球细丝水凝胶。
(3)将绒球细丝水凝胶在73℃下进行真空干燥6.3h,得到绒球细丝,然后置于氮气气氛下(流量为20mL/min),先在462℃下进行一次烧结3.1h,再升高温度至665℃进行二次烧结5.5h,降温、洗涤、干燥、超声粉碎,得到硬碳复合负极材料。
实施例3
本实施例的硬碳复合负极材料的制备方法,包括以下步骤:
(1)将植物绒球(pompon)置于氮气气氛下90℃干燥处理3.5h,将干燥后的绒球、0.13wt%氨甲基三甲基硅烷溶液按固液比为4.6g:100mL混合,得到均质绒球液,将均质绒球液进行剪切细丝化处理6次(每次处理时间为18min),得到均质绒球细丝液(细丝直径<10μm)。
(2)将均质绒球细丝液与LiClO(LiClO加入量为均质绒球细丝的1.6wt%)进行混合,并加LiAlO
2+LiSnO
2+LiOH混合物(其中,Li含量在0.066mol/L)进行锂碱氧化处理5.8h(pH为9.6),得到氧化后的均质绒球细丝液,将氧化后的均质绒球细丝液送至搅拌器,将0.4g醋酸锂加入搅拌器中,搅拌,分层,分离,取上层悬浮物质,得到绒球细丝水凝胶。
(3)将绒球细丝水凝胶在75℃下进行真空干燥6.5h,得到绒球细丝,然后置于氮气气氛下(流量为32mL/min),先在462℃下进行一次烧结3h,再升高温度至823℃进行二次烧结3.6h,降温、洗涤、干燥、超声粉碎,得到硬碳复合负极材料。
实施例4
本实施例的硬碳复合负极材料的制备方法,包括以下步骤:
(1)将植物绒球(pompon)置于氮气气氛下85℃干燥处理3.5h,将干燥后的绒球、0.023wt%氨甲基三甲基硅烷溶液按固液比为1.2g:100mL混合,得到均质绒球液,将均质绒球液进行剪切细丝化处理6次(每次处理时间为16min),得到均质绒球细丝液(细丝直径<10μm)。
(2)将均质绒球细丝液与LiClO(LiClO加入量为均质绒球细丝的1.6wt%)进行混合,并加LiAlO
2+Li
2SiO
3+LiSnO
2+LiOH混合物(其中,Li含量在0.072mol/L)进行锂碱氧化处理5h(pH为10.2),得到氧化后的均质绒球细丝液,将氧化后的均质绒球细丝液送至搅拌器,将0.4g醋酸锂加入搅拌器中,搅拌,分层,分离,取上层悬浮物质,得到绒球细丝水凝胶。
(3)将绒球细丝水凝胶在65℃下进行真空干燥6.5h,得到绒球细丝,然后置于氮气气氛下(流量为45mL/min),先在462℃下进行一次烧结3h,再升高温度至867℃进行二次烧 结5.4h,降温、洗涤、干燥、超声粉碎,得到硬碳复合负极材料。
对比例1(没有加入碱液进行锂碱氧化处理)
本对比例的硬碳复合负极材料的制备方法,包括以下步骤:
(1)将植物绒球(pompon)置于氮气气氛下85℃干燥处理3.5h,将干燥后的绒球、3.5wt%的乙醇溶液按固液比为4.1g:100mL混合,得到均质绒球液,将均质绒球液进行剪切细丝化处理6次(每次处理时间为20min),得到均质绒球细丝液(细丝直径<10μm)。
(2)将均质绒球细丝液与LiClO(LiClO加入量为均质绒球细丝的0.86wt%)进行混合,得到氧化后的均质绒球细丝液,将氧化后的均质绒球细丝液送至搅拌器,将0.35g醋酸锂加入搅拌器中,搅拌,分层,分离,取上层悬浮物质,得到绒球细丝水凝胶。
(3)将绒球细丝水凝胶在73℃下进行真空干燥6.3h,得到绒球细丝,然后置于氮气气氛下(流量为20mL/min),先在462℃下进行一次烧结3.1h,再升高温度至665℃进行二次烧结5.5h,降温、洗涤、干燥、超声粉碎,得到硬碳复合负极材料。
对比例2(分散剂为乙醇溶液)
本对比例的硬碳复合负极材料的制备方法,包括以下步骤:
(1)将植物绒球(pompon)置于氮气气氛下95℃干燥处理3.5h,将干燥后的绒球、3.5wt%的乙醇溶液按固液比为4.1g:100mL混合,得到均质绒球液,将均质绒球液进行剪切细丝化处理6次(每次处理时间为18min),得到均质绒球细丝液(细丝直径<10μm)。
(2)将均质绒球细丝液与LiClO(LiClO加入量为均质绒球细丝的1.6wt%)进行混合,并加LiAlO
2+LiSnO
2+LiOH混合物(其中,Li含量在0.066mol/L)进行锂碱氧化处理5.8h(pH为9.6),得到氧化后的均质绒球细丝液,将氧化后的均质绒球细丝液送至搅拌器,将0.35g醋酸锂加入搅拌器中,搅拌,分层,分离,取上层悬浮物质,得到绒球细丝水凝胶。
(3)将绒球细丝水凝胶在75℃下进行真空干燥6.5h,得到绒球细丝,然后置于氮气气氛下(流量为32mL/min),先在462℃下进行一次烧结3h,再升高温度至823℃进行二次烧结3.6h,降温、洗涤、干燥、超声粉碎,得到硬碳复合负极材料。
应用例:
将实施例1-4、对比例1-2制得的硬碳复合负极材料、乙炔黑和聚偏氟乙稀按照质量比为8:1:1的比例溶解在N-甲基吡咯烷酮中,研磨形成膏状活性材料,然后将膏状活性材料均匀地涂抹在Cu箔基底上,放入真空烘箱中,在85℃下干燥8h制成电极片,将锂片作为对电极,电解液为1mol/L六氟磷酸锂(LiPF6)的EC/DMC/DEC(质量比为1:1:1的混合溶液),在手套箱中组装成CR2025型扣式电池,在LAND型电池测试系统上,于0.1A/g电流密度, 0.01-3V下进行电化学能测试。
表1为实施例1、2、3、4与对比例1、2制备的样品的比表面积对比,发现实施例的样品比表面积较对比例高。
表1实施例与对比例的比表面积测试数据
样品 | 比表面积(m 2/g) |
实施例1 | 11.02 |
实施例2 | 12.17 |
实施例3 | 12.87 |
实施例4 | 13.63 |
对比例1 | 8.16 |
对比例2 | 10.15 |
电化学性能:
表2为实施例1、2、3、4与对比例1、2制备的样品的电化学性能对比,从实施例中发现,随着烧结过程中氮气流量的增加,所制备的材料的比容量及首效均有所升高,利用本发明的方法制备的实施例的比容量及首效高于对比例。
表2实施例与对比例的电化学性能测试数据
样品 | 脱锂比容量(mAh g -1) | 首效(%) |
实施例1 | 330.5 | 71.75 |
实施例2 | 332.8 | 73.19 |
实施例3 | 340.7 | 75.29 |
实施例4 | 331.6 | 72.19 |
对比例1 | 300.1 | 50.12 |
对比例2 | 308.2 | 61.69 |
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (10)
- 一种硬碳复合负极材料,其特征在于,包括以下原料:植物绒球、氧化剂、锂源、分散剂和含羧基的锂盐;所述锂源为LiAlO 2、Li 2SiO 3、LiSnO 2中的至少一种。
- 根据权利要求1所述的硬碳复合负极材料,其特征在于,所述分散剂为氨甲基三甲基硅烷溶液、N-β-(氨乙基)-γ-氨丙基甲基二甲氧基硅烷中的一种。
- 根据权利要求1所述的硬碳复合负极材料,其特征在于,所述氧化剂为LiClO;所述含羧基的锂盐为醋酸锂。
- 根据权利要求1所述的硬碳复合负极材料,其特征在于,所述植物绒球为白酒草、蒲公英、朱缨花或藿香蓟中的至少一种。
- 根据权利要求1所述的硬碳复合负极材料,其特征在于,所述硬碳复合负极材料的比表面积为10-15m 2/g。
- 根据权利要求1所述的硬碳复合负极材料,其特征在于,所述硬碳复合负极材料的脱锂比容量为330.5-340mAh g -1;首效为71-76%。
- 权利要求1-6任一项所述的硬碳复合负极材料的制备方法,其特征在于,包括以下步骤:(1)将植物绒球和分散剂混合,再进行均质处理,得到均质绒球细丝液;(2)将所述均质绒球细丝液、氧化剂、锂源和碱液混合,进行锂碱氧化处理,再加入含羧基的锂盐,进行接枝反应,搅拌分层,分离,取上层悬浮物质,得到绒球细丝水凝胶;(3)将所述绒球细丝水凝胶进行干燥,进行一次烧结,升温,进行二次烧结,得到所述硬碳复合负极材料。
- 根据权利要求7所述的制备方法,其特征在于,步骤(2)中,所述碱液为LiOH溶液;所述含羧基的锂盐为醋酸锂。
- 根据权利要求7所述的制备方法,其特征在于,步骤(3)中,所述一次烧结的温度为400~500℃,一次烧结的时间为2~6h;所述二次烧结的温度为500-1200℃,二次烧结的时间为2~6h。
- 权利要求1-6任一项所述的硬碳复合负极材料在制备电池、催化剂或超级电容器中的应用。
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