CN105702945B - Liquid phase in-situ reducing-cold quenching preparation method and applications of composite negative pole material - Google Patents
Liquid phase in-situ reducing-cold quenching preparation method and applications of composite negative pole material Download PDFInfo
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- CN105702945B CN105702945B CN201610118636.5A CN201610118636A CN105702945B CN 105702945 B CN105702945 B CN 105702945B CN 201610118636 A CN201610118636 A CN 201610118636A CN 105702945 B CN105702945 B CN 105702945B
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 239000007791 liquid phase Substances 0.000 title claims abstract description 13
- 238000010791 quenching Methods 0.000 title claims description 9
- 230000000171 quenching effect Effects 0.000 title claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 78
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 229910001439 antimony ion Inorganic materials 0.000 claims abstract description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 229910001432 tin ion Inorganic materials 0.000 claims abstract 2
- 239000012266 salt solution Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical group Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- -1 graphene Compound Chemical class 0.000 claims 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims 1
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 239000012279 sodium borohydride Substances 0.000 claims 1
- 229910000033 sodium borohydride Inorganic materials 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 abstract description 48
- 238000000034 method Methods 0.000 abstract description 18
- 238000001816 cooling Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 13
- 229910045601 alloy Inorganic materials 0.000 abstract description 12
- 239000000956 alloy Substances 0.000 abstract description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 229910052786 argon Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004448 titration Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000010405 anode material Substances 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 150000001462 antimony Chemical class 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910020646 Co-Sn Inorganic materials 0.000 description 2
- 229910020712 Co—Sb Inorganic materials 0.000 description 2
- 229910020709 Co—Sn Inorganic materials 0.000 description 2
- 229910020935 Sn-Sb Inorganic materials 0.000 description 2
- 229910008336 SnCo Inorganic materials 0.000 description 2
- 229910006913 SnSb Inorganic materials 0.000 description 2
- 229910008757 Sn—Sb Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001325 element alloy Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了复合负极材料的液相原位还原‑冷淬制备方法，以石墨为原料，采用改性Hummers法制备氧化石墨，将氧化石墨超声分散于锡离子、锑离子和钴离子的溶液中，通过原位合成工艺，采用滴定还原法，通过还原剂将氧化石墨还原成石墨烯的同时原位生成SnSbCo合金，并加入液氮进行冷淬处理使得石墨烯牢固包裹纳米合金颗粒，氩气保护条件，在一定温度下煅烧后，制备得到SnSbCo/石墨烯复合负极材料。相对于现有技术，本发明的制备方法有效提高材料制备效率和结构稳定性；采用本发明的材料组装得到的钠离子电池具有高充放电比容量、良好的倍率性能和循环性能。
The invention discloses a liquid-phase in-situ reduction-cooling preparation method for a composite negative electrode material, using graphite as a raw material, adopting a modified Hummers method to prepare graphite oxide, and ultrasonically dispersing the graphite oxide in a solution of tin ions, antimony ions and cobalt ions , through the in-situ synthesis process, using the titration reduction method, the graphite oxide is reduced to graphene through the reducing agent, and the SnSbCo alloy is generated in situ, and liquid nitrogen is added for cooling to make the graphene firmly wrap the nano-alloy particles, and the argon protection Conditions, after calcining at a certain temperature, the SnSbCo/graphene composite negative electrode material is prepared. Compared with the prior art, the preparation method of the invention effectively improves the material preparation efficiency and structural stability; the sodium ion battery assembled by using the material of the invention has high charge-discharge specific capacity, good rate performance and cycle performance.
Description
技术领域technical field
本发明涉及新能源技术领域，尤其涉及复合负极材料的液相原位还原-冷淬制备方法及其应用。The invention relates to the technical field of new energy, in particular to a liquid-phase in-situ reduction-cooling preparation method and application of a composite negative electrode material.
背景技术Background technique
目前，能源的储存和转换已成为制约世界经济可持续发展的重要问题。锂离子电池由于其具备高电压、高比能量、自放电小和循环寿命长等优势，在便携式电源应用中得到长足发展。同为第I主族的钠离子和锂离子的性质有许多相似之处，虽然钠离子电池研究进展缓慢，但随着储能电源和电动汽车的逐步发展，全球的锂资源将无法有效的满足动力锂离子电池的巨大需求，从而将进一步推高与锂相关材料的价格，增大电池成本，最终阻碍新能源产业的发展。相反，钠离子电池因其原料储量丰富(比锂高4～5个数量级)、价格便宜、对环境绿色友好等特点而逐渐成为研究热点，被广泛认为是下一代储能和动力电池的理想选择。At present, the storage and conversion of energy has become an important issue restricting the sustainable development of the world economy. Due to its advantages of high voltage, high specific energy, small self-discharge and long cycle life, lithium-ion batteries have made great progress in portable power applications. The properties of sodium ions and lithium ions, which are both in the main group I, have many similarities. Although the research on sodium ion batteries is progressing slowly, with the gradual development of energy storage power sources and electric vehicles, the global lithium resources will not be able to effectively meet The huge demand for power lithium-ion batteries will further push up the price of lithium-related materials, increase battery costs, and ultimately hinder the development of new energy industries. On the contrary, sodium-ion batteries have gradually become a research hotspot due to their abundant raw material reserves (4 to 5 orders of magnitude higher than lithium), low price, and environmental friendliness, and are widely considered to be ideal for next-generation energy storage and power batteries. .
研究发现，Pb、Sn、Sb三种金属能与钠离子发生金属合金化反应。由于Pb属重金属材料，污染性大未被广泛研究，而Na15Sn4、Na3Sb合金分别可提供高达847mAh/g、660mAh/g的理论比容量，是潜在高容量的钠离子电池负极材料。Xiao等研究人员报道了钠离子电池SnSb/C负极材料，在55mA/g的电流密度下充放电循环125周后，比容量稳定在525mAh/g并且库伦效率达到97％(L.Xiao,Y.Cao,J.Xiao,et al.Chemical Communications,2012,48:3321-3323)。金属Sn电极在前两个循环的比容量可达460mAh/g，但是到第三个循环，比容量会衰减到163mAh/g。金属Sb电极同样出现了快速的比容量衰减，20个循环后，容量迅速从342mAh/g衰减到100mAh/g以下。可见两种电极都对Na有极差的可循环性。Sn/C电极在经过13个循环后，比容量降到了初始容量的20％，而Sb/C电极在前30个循环都很稳定，可逆比容量从494mAh/g减小到397mAh/g，容量保持率达到80.4％，不过在50个循环后，容量迅速衰减至100mAh/g。Lin等研究人员采用表面活性剂辅助湿化学法制备了钠离子电池Sn0.9Cu0.1负极材料，在169mA/g的电流密度下，充放电循环100周后，容量稳定在420mAh/g，容量保持率为97％，表现出高循环稳定性，而纯Sn负极材料在相同的充放电条件下，纳米级Sn和微米级Sn的容量分别只剩250mAh/g和66mAh/g(Y.M.Lin,Paul R.Abel,A.Gupta,et al.ACSAppl.Mater.Interfaces,2013,5,8273-8277)。The study found that Pb, Sn, Sb three metals can undergo metal alloying reaction with sodium ions. Since Pb is a heavy metal material, it is highly polluting and has not been widely studied. However, Na 15 Sn 4 and Na 3 Sb alloys can provide theoretical specific capacities as high as 847mAh/g and 660mAh/g, respectively, and are potentially high-capacity anode materials for sodium-ion batteries. . Xiao and other researchers reported that the SnSb/C anode material for sodium-ion batteries, after 125 cycles of charge-discharge cycles at a current density of 55mA/g, the specific capacity was stable at 525mAh/g and the Coulombic efficiency reached 97% (L. Xiao, Y. Cao, J. Xiao, et al. Chemical Communications, 2012, 48:3321-3323). The specific capacity of the metal Sn electrode can reach 460mAh/g in the first two cycles, but the specific capacity will decay to 163mAh/g in the third cycle. The metal Sb electrode also exhibited rapid specific capacity decay, and the capacity rapidly decayed from 342mAh/g to less than 100mAh/g after 20 cycles. It can be seen that both electrodes have extremely poor recyclability to Na. After 13 cycles, the specific capacity of the Sn/C electrode dropped to 20% of the initial capacity, while the Sb/C electrode was stable in the first 30 cycles, and the reversible specific capacity decreased from 494mAh/g to 397mAh/g. The retention rate reached 80.4%, but the capacity rapidly decayed to 100mAh/g after 50 cycles. Researchers such as Lin prepared Sn 0.9 Cu 0.1 anode materials for sodium-ion batteries by a surfactant-assisted wet chemical method. At a current density of 169mA/g, after 100 cycles of charge-discharge cycles, the capacity was stable at 420mAh/g, and the capacity retention rate 97%, showing high cycle stability, and pure Sn negative electrode material under the same charge and discharge conditions, the capacity of nano-scale Sn and micro-scale Sn are only 250mAh/g and 66mAh/g (YMLin, Paul R.Abel , A. Gupta, et al. ACS Appl. Mater. Interfaces, 2013, 5, 8273-8277).
为了解决这一问题，Yui等研究人员提出了掺入Co，能使SnCo二元合金的电化学性能优越于单质Sn，同样循环30周，SnCo的容量保持在300mAh/g左右，而单质Sn负极材料基本丧失活性(Y.Yui,Y.Ono,M.Hayashi,et al.Journal of the Electrochemical Society,2015,162:A3098-A3102)。但是，该二元合金的电化学性能仍旧不能满足现有要求。In order to solve this problem, researchers such as Yui proposed the doping of Co, which can make the electrochemical performance of the SnCo binary alloy superior to that of simple Sn. After 30 cycles of the same cycle, the capacity of SnCo remained at about 300mAh/g, while the single Sn negative electrode The material basically loses its activity (Y.Yui, Y.Ono, M.Hayashi, et al.Journal of the Electrochemical Society, 2015, 162:A3098-A3102). However, the electrochemical performance of the binary alloy still cannot meet the existing requirements.
石墨烯因具备表面积大、导电率优越及良好的机械强度的特点而被广泛应用于电极材料的改性研究。通过化学氧化还原得到的石墨烯拥有高度缺陷，反而提高了其导电率，比如采用改性Hummers法制备氧化石墨(GO)，再利用化学还原去除含氧官能团得到还原氧化石墨烯(rGO)，因其具备高电导率(16000S m-1)而同样备受瞩目。与石墨烯类似，rGO表现出高弹性、高导电率而作为基底材料开始逐渐应用于钠离子电池。Nithya通过化学还原法制备了Sb/rGO，131mA/g的电流密度下循环50周，容量维持在598mAh/g，rGO作为基底，使材料结构更加稳固(C.Nithya,S.Gopukumar.J.Mater.Chem.A.,2014,2:10516-10525)。因而，有必要对钠离子电池进行复合负极材料的进一步研究，以提高电极材料的充放电比容量以及改善其循环性能。Graphene has been widely used in the modification of electrode materials due to its large surface area, superior electrical conductivity and good mechanical strength. Graphene obtained by chemical redox has a high degree of defect, but its conductivity is improved. For example, graphite oxide (GO) is prepared by modified Hummers method, and then the oxygen-containing functional group is removed by chemical reduction to obtain reduced graphene oxide (rGO). It is also notable for its high electrical conductivity (16000S m -1 ). Similar to graphene, rGO exhibits high elasticity and high conductivity, and has been gradually applied to sodium-ion batteries as a substrate material. Nithya prepared Sb/rGO by chemical reduction method, cycled for 50 cycles at a current density of 131mA/g, the capacity was maintained at 598mAh/g, and rGO was used as a substrate to make the material structure more stable (C.Nithya, S.Gopukumar.J.Mater Chem.A., 2014, 2:10516-10525). Therefore, it is necessary to conduct further research on composite negative electrode materials for sodium-ion batteries in order to increase the charge-discharge specific capacity of electrode materials and improve their cycle performance.
发明内容Contents of the invention
本发明为解决现有技术中存在的不足，提供一种以石墨烯(rGO)为基底材料，在二元合金SnSb基础上引入第三种元素Co，制备出具有高充放电比容量、良好倍率性能的SnSbCo/石墨烯复合负极材料。In order to solve the deficiencies in the prior art, the present invention provides a graphene (rGO) as the base material, and introduces the third element Co on the basis of the binary alloy SnSb, and prepares a battery with high charge-discharge specific capacity and good rate performance of SnSbCo/graphene composite anode materials.
本发明的目的是通过以下技术方实现的：The purpose of the present invention is achieved by the following technical side:
复合负极材料的液相原位还原-冷淬制备方法，包括以下步骤：The liquid-phase in-situ reduction-cooling preparation method of the composite negative electrode material comprises the following steps:
(1)将锡盐、锑盐和钴盐溶解于溶剂中，得到混合盐溶液；将氧化石墨超声分散于混合盐溶液中；(1) dissolving tin salt, antimony salt and cobalt salt in a solvent to obtain a mixed salt solution; ultrasonically dispersing graphite oxide in the mixed salt solution;
(2)将还原剂溶解于溶剂中，得到还原溶液；将还原溶液滴加入步骤(1)的混合盐溶液中并持续搅拌；滴加结束后，得到浑浊液，将浑浊液于50-80℃搅拌反应；(2) Dissolve the reducing agent in the solvent to obtain a reducing solution; add the reducing solution dropwise to the mixed salt solution in step (1) and continue to stir; stirring reaction;
(3)向步骤(2)的浑浊液中加入液氮快速冷淬后，真空抽滤、多次洗涤后冷冻干燥或真空干燥，得到SnSbCo/石墨烯前驱体粉末；(3) After adding liquid nitrogen to the turbid solution of step (2) for rapid cooling, vacuum filtration, freeze-drying or vacuum drying after multiple washings, to obtain SnSbCo/graphene precursor powder;
(4)惰性气体保护下，将前驱体粉末以一定升温速率升温至200-450℃下恒温煅烧，得到SnSbCo/石墨烯复合负极材料。(4) Under the protection of an inert gas, the precursor powder is heated at a certain heating rate to 200-450° C. and calcined at a constant temperature to obtain a SnSbCo/graphene composite negative electrode material.
相对于现有技术，本发明通过原位合成工艺，采用滴定还原法在制备石墨烯的同时形成纳米SnSbCo多元合金颗粒，有效提高材料制备效率；加入液氮急速冷却，通过冷淬工艺使片状石墨烯牢固的包裹SnSbCo合金颗粒，有效提高电极材料的结构稳定性。Compared with the prior art, the present invention adopts an in-situ synthesis process to form nano-SnSbCo multi-element alloy particles while preparing graphene by titration reduction method, which effectively improves the material preparation efficiency; adding liquid nitrogen for rapid cooling, and making flakes through a quenching process Graphene firmly wraps the SnSbCo alloy particles, effectively improving the structural stability of the electrode material.
进一步，步骤(1)所述混合盐溶液中，锡盐的浓度为0.01-0.5mol/L，锑盐的浓度为0.01-0.5mol/L，钴盐的浓度为0.001-0.05mol/L；锡离子、锑离子、钴离子的摩尔比为1:1:0.1。Further, in the mixed salt solution described in step (1), the concentration of the tin salt is 0.01-0.5mol/L, the concentration of the antimony salt is 0.01-0.5mol/L, and the concentration of the cobalt salt is 0.001-0.05mol/L; The molar ratio of ions, antimony ions, and cobalt ions is 1:1:0.1.
进一步，步骤(3)中加入液氮的体积与步骤(2)中浑浊液的体积比为0.5:1-2:1。Further, the volume ratio of the liquid nitrogen added in step (3) to the turbid liquid in step (2) is 0.5:1-2:1.
进一步，步骤(1)得到的混合盐溶液中，氧化石墨的浓度为0.5-2mg/mL。Further, in the mixed salt solution obtained in step (1), the concentration of graphite oxide is 0.5-2 mg/mL.
进一步，步骤(2)中还原溶液的浓度为0.1-2mol/L；所述还原剂为水合肼、氨水、NaBH4和HI中的一种。Further, the concentration of the reducing solution in step (2) is 0.1-2mol/L; the reducing agent is one of hydrazine hydrate, ammonia water, NaBH 4 and HI.
进一步，步骤(1)中超声的功率为100-200W；步骤(2)中的滴加速度为1-3mL/min；步骤(2)中的搅拌速度为200-1000r/min。Further, the ultrasonic power in step (1) is 100-200W; the dropping rate in step (2) is 1-3mL/min; the stirring speed in step (2) is 200-1000r/min.
进一步，所述锡盐为氯化亚锡或醋酸亚锡，所述锑盐为氯化锑或醋酸锑，所述钴盐为氯化钴或醋酸钴；步骤(1)和步骤(2)中所述溶剂为去离子水、乙醇中的任意一种或二者混合的溶剂。Further, the tin salt is stannous chloride or stannous acetate, the antimony salt is antimony chloride or antimony acetate, and the cobalt salt is cobalt chloride or cobalt acetate; in step (1) and step (2) The solvent is any one of deionized water, ethanol or a mixed solvent of the two.
本发明还提供了一种钠离子电池的制备方法，包括以下步骤：将SnSbCo/石墨烯复合负极材料、导电炭黑、粘结剂按照质量比为(50-80)：(30-10)：(20-10)混合均匀后涂覆在铜箔上，真空干燥，辊压后切片，得到圆形电极片；将电极片、金属钠片、电解液组装成钠离子电池。所述SnSbCo/石墨烯复合负极材料为上述提及的任意方法制备得到的SnSbCo/石墨烯复合负极材料。The present invention also provides a preparation method of a sodium ion battery, comprising the following steps: the SnSbCo/graphene composite negative electrode material, conductive carbon black, and binder are (50-80): (30-10) according to the mass ratio: (20-10) Mix evenly and coat on the copper foil, vacuum dry, roll and slice to obtain a circular electrode sheet; assemble the electrode sheet, metal sodium sheet, and electrolyte to form a sodium ion battery. The SnSbCo/graphene composite negative electrode material is the SnSbCo/graphene composite negative electrode material prepared by any of the methods mentioned above.
相对于现有技术，采用本发明的材料组装得到的钠离子电池具有高充放电比容量、良好的倍率性能和循环性能。Compared with the prior art, the sodium ion battery assembled by using the material of the invention has high charge-discharge specific capacity, good rate performance and cycle performance.
进一步，所述粘结剂为LA132、聚偏二氟乙烯或CMC粘结剂中的一种；所述涂覆厚度为60-120μm；所述辊压的厚度为35-90μm。Further, the binder is one of LA132, polyvinylidene fluoride or CMC binder; the coating thickness is 60-120 μm; the rolling thickness is 35-90 μm.
本发明还提供了一种钠离子电池，包括圆形电极片、金属钠片和电解液，所述圆形电极片由SnSbCo/石墨烯复合负极材料、导电炭黑、粘结剂按照质量比为(50-80)：(30-10)：(20-10)混合均匀后涂覆在铜箔上，真空干燥，辊压后切片得到，所述SnSbCo/石墨烯复合负极材料为上述提及的任意方法制备得到的SnSbCo/石墨烯复合负极材料。The present invention also provides a sodium ion battery, comprising a circular electrode sheet, a metal sodium sheet and an electrolyte, wherein the circular electrode sheet is composed of a SnSbCo/graphene composite negative electrode material, conductive carbon black, and a binding agent according to a mass ratio of (50-80): (30-10): (20-10) coated on copper foil after mixing evenly, vacuum drying, rolling and slicing to obtain, the SnSbCo/graphene composite negative electrode material is the above-mentioned The SnSbCo/graphene composite negative electrode material prepared by any method.
相对于现有技术，本发明的钠离子电池采用本发明的SnSbCo/石墨烯复合负极材料，使得钠离子电池具有高充放电比容量、良好的倍率性能和循环性能。Compared with the prior art, the sodium ion battery of the present invention adopts the SnSbCo/graphene composite negative electrode material of the present invention, so that the sodium ion battery has high charge-discharge specific capacity, good rate performance and cycle performance.
为了更好地理解和实施，下面结合附图详细说明本发明。For better understanding and implementation, the present invention will be described in detail below in conjunction with the accompanying drawings.
附图说明Description of drawings
图1是实施例1制备得到的SnSbCo/石墨烯复合负极材料的XRD图谱。FIG. 1 is an XRD spectrum of the SnSbCo/graphene composite negative electrode material prepared in Example 1.
图2是实施例1制备得到的SnSbCo/石墨烯复合负极材料的SEM图。FIG. 2 is an SEM image of the SnSbCo/graphene composite negative electrode material prepared in Example 1. FIG.
图3是实施例1制备得到的SnSbCo/石墨烯复合负极材料的TEM图。3 is a TEM image of the SnSbCo/graphene composite negative electrode material prepared in Example 1.
图4是对比实施例制备得到的SnSbCo/石墨烯复合负极材料的XRD图谱。Fig. 4 is the XRD spectrum of the SnSbCo/graphene composite negative electrode material prepared in the comparative example.
图5是对比实施例制备得到的SnSbCo/石墨烯复合负极材料的SEM图。Fig. 5 is a SEM image of the SnSbCo/graphene composite negative electrode material prepared in the comparative example.
图6是对比实施例制备得到的SnSbCo/石墨烯复合负极材料的TEM图。Fig. 6 is a TEM image of the SnSbCo/graphene composite negative electrode material prepared in the comparative example.
图7是实施例1制备得到的SnSbCo/石墨烯复合负极材料组装的钠离子电池的恒流充放电性能图。7 is a constant current charge and discharge performance diagram of a sodium ion battery assembled with the SnSbCo/graphene composite negative electrode material prepared in Example 1.
图8是对比实施例制备得到的SnSbCo/石墨烯复合负极材料组装的钠离子电池的恒流充放电性能图。Fig. 8 is a constant current charge and discharge performance diagram of a sodium ion battery assembled with the SnSbCo/graphene composite negative electrode material prepared in the comparative example.
具体实施方式Detailed ways
本发明公开的复合负极材料的液相原位还原-冷淬制备方法，包括以下步骤：The liquid-phase in-situ reduction-cooling preparation method of the composite negative electrode material disclosed by the present invention comprises the following steps:
(1)将锡盐、锑盐和钴盐溶解于溶剂中，得到混合盐溶液；将氧化石墨超声分散于混合盐溶液中；(1) dissolving tin salt, antimony salt and cobalt salt in a solvent to obtain a mixed salt solution; ultrasonically dispersing graphite oxide in the mixed salt solution;
(2)将还原剂溶解于溶剂中，得到还原溶液；将还原溶液滴加入步骤(1)的混合盐溶液中并持续搅拌；滴加结束后，得到浑浊液，将浑浊液于50-80℃搅拌反应1-12h；(2) Dissolve the reducing agent in the solvent to obtain a reducing solution; add the reducing solution dropwise to the mixed salt solution in step (1) and continue to stir; Stir the reaction for 1-12h;
(3)向步骤(2)的浑浊液中加入液氮快速冷淬后，真空抽滤、多次洗涤后进行真空干燥或冷冻干燥，得到SnSbCo/石墨烯前驱体粉末；(3) After adding liquid nitrogen to the turbid solution of step (2) for rapid cooling, vacuum filtration, repeated washing, vacuum drying or freeze drying, to obtain SnSbCo/graphene precursor powder;
(4)惰性气体保护下，将前驱体粉末以一定升温速率升温至200-450℃下恒温煅烧2-6h，得到SnSbCo/石墨烯复合负极材料。(4) Under the protection of an inert gas, the precursor powder is heated at a certain heating rate to 200-450° C. and calcined at a constant temperature for 2-6 hours to obtain a SnSbCo/graphene composite negative electrode material.
其中，步骤(1)的混合盐溶液中，锡盐的浓度为0.01-0.5mol/L，锑盐的浓度为0.01-0.5mol/L，钴盐的浓度为0.001-0.05mol/L；锡离子、锑离子、钴离子的摩尔比为1:1:0.1；步骤(1)得到的混合盐溶液中，氧化石墨的浓度为0.5-2mg/mL。Wherein, in the mixed salt solution of step (1), the concentration of tin salt is 0.01-0.5mol/L, the concentration of antimony salt is 0.01-0.5mol/L, and the concentration of cobalt salt is 0.001-0.05mol/L; The molar ratio of antimony ions and cobalt ions is 1:1:0.1; in the mixed salt solution obtained in step (1), the concentration of graphite oxide is 0.5-2mg/mL.
步骤(1)中超声的功率为100-200W。The power of ultrasound in step (1) is 100-200W.
步骤(2)中所述还原剂为水合肼、氨水、NaBH4和HI中的任意一种；所述还原剂的浓度为0.1-2mol/L。The reducing agent in the step (2) is any one of hydrazine hydrate, ammonia water, NaBH 4 and HI; the concentration of the reducing agent is 0.1-2mol/L.
步骤(1)和步骤(2)中所述溶剂为去离子水、乙醇中的任意一种或者两种混合的溶剂。The solvent described in step (1) and step (2) is any one of deionized water, ethanol or a mixed solvent of both.
步骤(3)中液氮的体积与步骤(2)中浑浊液的体积比为0.5:1-2:1。The volume ratio of the liquid nitrogen in step (3) to the turbid liquid in step (2) is 0.5:1-2:1.
步骤(3)中真空干燥温度为50-80℃，时间为10-24h。In step (3), the vacuum drying temperature is 50-80°C and the time is 10-24h.
步骤(3)中冷冻干燥温度为-45℃，压力为0.37Pa，时间为40-70h。In step (3), the freeze-drying temperature is -45°C, the pressure is 0.37Pa, and the time is 40-70h.
步骤(4)中所述的升温速率为1-10℃/min。The heating rate described in step (4) is 1-10° C./min.
实施例1Example 1
本实施例中，复合负极材料的液相原位还原-冷淬制备方法，包括以下步骤：In this embodiment, the liquid-phase in-situ reduction-cooling preparation method of the composite negative electrode material includes the following steps:
(1)称取0.001mol的SnCl2，0.001mol的SbCl3，0.0001mol的CoCl2·6H2O和0.0032mol C6H5Na3O7·2H2O，并完全溶解于100mL的去离子水中，得到混合盐溶液。将0.1g氧化石墨超声分散于混合盐溶液中，其中所述超声功率为150W。(1) Weigh 0.001 mol of SnCl 2 , 0.001 mol of SbCl 3 , 0.0001 mol of CoCl 2 6H 2 O and 0.0032 mol of C 6 H 5 Na 3 O 7 2H 2 O, and dissolve them completely in 100 mL of deionized water to obtain a mixed salt solution. 0.1 g of graphite oxide was ultrasonically dispersed in the mixed salt solution, wherein the ultrasonic power was 150W.
(2)用NaOH调节0.1mol/L的还原剂NaBH4水溶液，使其pH≥12；将pH≥12的300mL的0.1mol/L的NaBH4水溶液缓慢滴加至步骤(1)中的混合盐溶液中并持续搅拌；滴加结束后，得到浑浊液，将浑浊液在80℃下加热5h。其中NaBH4水溶液的滴加速度为2mL/min，搅拌速度为800r/min。(2) Regulate the 0.1mol/L reducing agent NaBH 4 aqueous solution with NaOH, make it pH ≥ 12; Slowly add the 0.1 mol/L NaBH 4 aqueous solution of pH ≥ 12 to the mixed salt in step (1) solution and continued stirring; after the dropwise addition, a cloudy solution was obtained, and the cloudy solution was heated at 80°C for 5h. Wherein the NaBH The rate of addition of the aqueous solution is 2mL/min, and the stirring speed is 800r/min.
(3)按照液氮体积与步骤(2)中浑浊液的体积比为0.5:1，向步骤(2)的浑浊液中加入200mL液氮后，真空抽滤，并将抽滤得到的沉淀物依次用去离子水、无水乙醇多次洗涤后进行冷冻干燥，得到SnSbCo/石墨烯前驱体粉末；然后将前驱体粉末置于管式炉中，在氩气保护条件下，300℃恒温煅烧4h，得到SnSbCo/石墨烯复合负极材料。其中，冷冻干燥的条件为0.37Pa和-45℃，冷冻干燥时间为40h；管式炉的升温速率为2℃/min。(3) According to the volume ratio of the volume of liquid nitrogen to the turbid liquid in step (2) of 0.5:1, after adding 200mL of liquid nitrogen to the turbid liquid in step (2), vacuum filter, and the precipitate obtained by suction filtration SnSbCo/graphene precursor powder was obtained by washing with deionized water and absolute ethanol several times in turn, and then freeze-drying; then the precursor powder was placed in a tube furnace and calcined at a constant temperature of 300 °C for 4 h under the protection of argon. , to obtain SnSbCo/graphene composite anode material. Among them, the freeze-drying conditions are 0.37Pa and -45°C, and the freeze-drying time is 40h; the heating rate of the tube furnace is 2°C/min.
步骤(2)中所述还原剂还可选用水合肼、氨水或HI。The reducing agent described in step (2) can also choose hydrazine hydrate, ammonia water or HI.
在本实施例中，氧化石墨的制备方法如下：将2g天然鳞片石墨和2g硝酸钠加入至预先冷却至0℃的110mL的浓硫酸中，在冰浴条件下持续搅拌15-30min；在冰浴条件下缓慢加入12g高锰酸钾，搅拌20-40min，然后在室温下持续搅拌48h；缓慢加入184mL去离子水，搅拌150min；再加入560mL温度为50-60℃的去离子水和50mL过氧化氢溶液搅拌25min，用稀盐酸多次离心洗涤后冷冻干燥得到氧化石墨。制备氧化石墨的方法不局限于此，其他可以制备得到氧化石墨的方法均可。In this example, the preparation method of graphite oxide is as follows: add 2g of natural flake graphite and 2g of sodium nitrate to 110mL of concentrated sulfuric acid pre-cooled to 0°C, and keep stirring for 15-30min under ice bath conditions; Slowly add 12g of potassium permanganate under conditions, stir for 20-40min, then continue to stir at room temperature for 48h; slowly add 184mL of deionized water, stir for 150min; then add 560mL of deionized water at a temperature of 50-60℃ and 50mL of peroxide The hydrogen solution was stirred for 25 min, washed with dilute hydrochloric acid for several times, and freeze-dried to obtain graphite oxide. The method for preparing graphite oxide is not limited thereto, and any other method for preparing graphite oxide is acceptable.
本实施例还提供了一种使用所述SnSbCo/石墨烯复合负极材料制备的钠离子电池。具体的，将SnSbCo/石墨烯复合负极材料、导电炭黑、粘结剂按照质量比为5:3:2混合均匀后，在铜箔上涂覆成厚度为100μm的均匀薄层，在真空80℃下干燥12h，辊压后切成圆形电极片。将圆形电极片、金属钠片、1mol/L的NaClO4/EC/DEC电解液组装成钠离子电池。在本实施例中，所述粘结剂为CMC粘结剂，所述薄层辊压后的厚度为70μm，所述圆形电极片的直径为18mm。This embodiment also provides a sodium ion battery prepared by using the SnSbCo/graphene composite negative electrode material. Specifically, after the SnSbCo/graphene composite negative electrode material, conductive carbon black, and binder are mixed uniformly according to the mass ratio of 5:3:2, they are coated on a copper foil to form a uniform thin layer with a thickness of 100 μm. Dry at ℃ for 12 hours, roll and cut into circular electrode sheets. A sodium-ion battery is assembled by a circular electrode sheet, a metal sodium sheet, and 1mol/L NaClO 4 /EC/DEC electrolyte. In this embodiment, the adhesive is a CMC adhesive, the thickness of the thin layer after rolling is 70 μm, and the diameter of the circular electrode sheet is 18 mm.
在制备钠离子电池时，所述粘结剂还可选用LA132粘结剂或聚偏二氟乙烯粘结剂。When preparing the sodium ion battery, the binder can also be selected from LA132 binder or polyvinylidene fluoride binder.
实施例2Example 2
本实施例中，复合负极材料的液相原位还原-冷淬制备方法，包括以下步骤：In this embodiment, the liquid-phase in-situ reduction-cooling preparation method of the composite negative electrode material includes the following steps:
(1)称取0.02mol的醋酸亚锡，0.02mol的醋酸锑，0.002mol的醋酸钴和0.032molC6H5Na3O7·2H2O，并完全溶解于100mL的去离子水中，得到混合盐溶液。将0.05g氧化石墨超声分散于混合盐溶液中，其中所述超声功率为100W。(1) Weigh 0.02mol of stannous acetate, 0.02mol of antimony acetate, 0.002mol of cobalt acetate and 0.032mol of C 6 H 5 Na 3 O 7 2H 2 O, and dissolve them completely in 100mL of deionized water to obtain a mixed saline solution. 0.05 g of graphite oxide was ultrasonically dispersed in the mixed salt solution, wherein the ultrasonic power was 100W.
(2)用NaOH调节1mol/L的还原剂NaBH4水溶液，使其pH≥12；将pH≥12的300mL的1mol/L的NaBH4水溶液缓慢滴加至步骤(1)中的混合盐溶液中并持续搅拌；滴加结束后，得到浑浊液，将浑浊液在50℃下加热12h。其中NaBH4水溶液的滴加速度为1mL/min，搅拌速度为200r/min。(2) Regulate the 1mol/L reducing agent NaBH 4 aqueous solution with NaOH, make it pH ≥ 12; 300mL 1 mol/L NaBH 4 aqueous solution with pH ≥ 12 is slowly added dropwise to the mixed salt solution in step (1) And keep stirring; after the dropwise addition, a turbid solution was obtained, which was heated at 50° C. for 12 h. Wherein the NaBH 4 The rate of addition of the aqueous solution is 1mL/min, and the stirring speed is 200r/min.
(3)按照液氮体积与步骤(2)中浑浊液的体积比为1:1，向步骤(2)的浑浊液中加入400mL液氮后，真空抽滤，并将抽滤得到的沉淀物依次用去离子水、无水乙醇多次洗涤后进行真空干燥，得到SnSbCo/石墨烯前驱体粉末；然后将前驱体粉末置于管式炉中，在氩气保护条件下，450℃恒温煅烧2h，得到SnSbCo/石墨烯复合负极材料。其中，真空干燥的温度为50-80℃，干燥时间为10-24h；管式炉的升温速率为10℃/min。(3) According to the volume ratio of the volume of liquid nitrogen to the turbid liquid in step (2) of 1:1, after adding 400mL of liquid nitrogen to the turbid liquid in step (2), vacuum filtration, and the precipitate obtained by suction filtration After washing with deionized water and absolute ethanol for several times, vacuum drying was carried out to obtain the SnSbCo/graphene precursor powder; then the precursor powder was placed in a tube furnace and calcined at a constant temperature of 450 °C for 2 h under the protection of argon. , to obtain SnSbCo/graphene composite anode material. Wherein, the temperature of vacuum drying is 50-80° C., and the drying time is 10-24 hours; the heating rate of the tube furnace is 10° C./min.
步骤(2)中所述还原剂还可选用水合肼、氨水或HI。The reducing agent described in step (2) can also choose hydrazine hydrate, ammonia water or HI.
本实施例还提供了一种使用所述SnSbCo/石墨烯复合负极材料制备的钠离子电池。具体的，将SnSbCo/石墨烯复合负极材料、导电炭黑、粘结剂按照质量比为8:1:1混合均匀后，在铜箔上涂覆成厚度为120μm的均匀薄层，在真空50℃下干燥24h，辊压后切成圆形电极片。将圆形电极片、金属钠片、1mol/L的NaClO4/EC/DEC电解液组装成钠离子电池。在本实施例中，所述粘结剂为CMC粘结剂，所述薄层辊压后的厚度为35μm，所述圆形电极片的直径为18mm。This embodiment also provides a sodium ion battery prepared by using the SnSbCo/graphene composite negative electrode material. Specifically, after the SnSbCo/graphene composite negative electrode material, conductive carbon black, and binder are mixed uniformly according to the mass ratio of 8:1:1, they are coated on the copper foil to form a uniform thin layer with a thickness of 120 μm. Dry at ℃ for 24 hours, roll and cut into circular electrode sheets. A sodium-ion battery was assembled by circular electrode sheets, metal sodium sheets, and 1mol/L NaClO4/EC/DEC electrolyte. In this embodiment, the adhesive is a CMC adhesive, the thickness of the thin layer after rolling is 35 μm, and the diameter of the circular electrode sheet is 18 mm.
在制备钠离子电池时，所述粘结剂还可选用LA132粘结剂或聚偏二氟乙烯粘结剂。When preparing the sodium ion battery, the binder can also be selected from LA132 binder or polyvinylidene fluoride binder.
实施例3Example 3
本实施例中，复合负极材料的液相原位还原-冷淬制备方法，包括以下步骤：In this embodiment, the liquid-phase in-situ reduction-cooling preparation method of the composite negative electrode material includes the following steps:
(1)称取0.05mol的SnCl2，0.05mol的SbCl3，0.005mol的CoCl2·6H2O和0.032molC6H5Na3O7·2H2O，并完全溶解于100mL的去离子水中，得到混合盐溶液。将0.2g氧化石墨超声分散于混合盐溶液中，其中所述超声功率为200W。(1) Weigh 0.05mol of SnCl 2 , 0.05mol of SbCl 3 , 0.005mol of CoCl 2 6H 2 O and 0.032mol of C 6 H 5 Na 3 O 7 2H 2 O, and dissolve them completely in 100mL of deionized water , to obtain a mixed salt solution. 0.2 g of graphite oxide was ultrasonically dispersed in the mixed salt solution, wherein the ultrasonic power was 200W.
(2)用NaOH调节2mol/L的还原剂NaBH4水溶液，使其pH≥12；将pH≥12的300mL的2mol/L的NaBH4水溶液缓慢滴加至步骤(1)中的混合盐溶液中并持续搅拌；滴加结束后，得到浑浊液，将浑浊液在80℃下加热1h。其中NaBH4水溶液的滴加速度为3mL/min，搅拌速度为1000r/min。(2) Regulate 2mol/L reducing agent NaBH 4 aqueous solution with NaOH, make it pH ≥ 12; Slowly drop the 2 mol/L NaBH 4 aqueous solution of pH ≥ 12 into the mixed salt solution in step (1) And keep stirring; after the dropwise addition, a turbid solution is obtained, which is heated at 80° C. for 1 h. Wherein the NaBH The rate of addition of the aqueous solution is 3mL/min, and the stirring speed is 1000r/min.
(3)按照液氮体积与步骤(2)中浑浊液的体积比为2:1，向步骤(2)的浑浊液中加入800mL液氮后，真空抽滤，并将抽滤得到的沉淀物依次用去离子水、无水乙醇多次洗涤后进行冷冻干燥，得到SnSbCo/石墨烯前驱体粉末；然后将前驱体粉末置于管式炉中，在氩气保护条件下，200℃恒温煅烧6h，得到SnSbCo/石墨烯复合负极材料。其中，冷冻干燥的条件为0.37Pa和-45℃，冷冻干燥时间为70h；管式炉的升温速率为1℃/min。(3) According to the volume ratio of the volume of liquid nitrogen to the turbid liquid in step (2) of 2:1, after adding 800mL of liquid nitrogen to the turbid liquid in step (2), vacuum filter, and the precipitate obtained by suction filtration SnSbCo/graphene precursor powder was obtained by washing with deionized water and absolute ethanol several times in turn, and then freeze-drying. Then, the precursor powder was placed in a tube furnace and calcined at a constant temperature of 200 °C for 6 h under the protection of argon. , to obtain SnSbCo/graphene composite anode material. Among them, the freeze-drying conditions are 0.37Pa and -45°C, and the freeze-drying time is 70h; the heating rate of the tube furnace is 1°C/min.
步骤(2)中所述还原剂还可选用水合肼、氨水或HI。The reducing agent described in step (2) can also choose hydrazine hydrate, ammonia water or HI.
本实施例还提供了一种使用所述SnSbCo/石墨烯复合负极材料制备的钠离子电池。具体的，将SnSbCo/石墨烯复合负极材料、导电炭黑、粘结剂按照质量比为6:2:2混合均匀后，在铜箔上涂覆成厚度为60μm的均匀薄层，在真空60℃下干燥20h，辊压后切成圆形电极片。将圆形电极片、金属钠片、1mol/L的NaClO4/EC/DEC电解液组装成钠离子电池。在本实施例中，所述粘结剂为CMC粘结剂，所述薄层辊压后的厚度为90μm，所述圆形电极片的直径为18mm。This embodiment also provides a sodium ion battery prepared by using the SnSbCo/graphene composite negative electrode material. Specifically, after the SnSbCo/graphene composite negative electrode material, conductive carbon black, and binder are mixed uniformly according to the mass ratio of 6:2:2, they are coated on the copper foil to form a uniform thin layer with a thickness of 60 μm. Dry at ℃ for 20h, roll and cut into circular electrode sheets. A sodium-ion battery is assembled by a circular electrode sheet, a metal sodium sheet, and 1mol/L NaClO 4 /EC/DEC electrolyte. In this embodiment, the adhesive is a CMC adhesive, the thickness of the thin layer after rolling is 90 μm, and the diameter of the circular electrode sheet is 18 mm.
在制备钠离子电池时，所述粘结剂还可选用LA132粘结剂或聚偏二氟乙烯粘结剂。When preparing the sodium ion battery, the binder can also be selected from LA132 binder or polyvinylidene fluoride binder.
对比实施例comparative example
SnSbCo/石墨烯负极材料的制备方法，包括以下步骤：The preparation method of SnSbCo/graphene negative electrode material, comprises the following steps:
(1)称取0.001mol的SnCl2，0.001mol的SbCl3，0.0001mol的CoCl2·6H2O和0.032mol C6H5Na3O7·2H2O，并完全溶解于100mL的去离子水中，得到混合盐溶液。将0.05g氧化石墨超声分散于混合盐溶液中，其中所述超声功率为100W。(1) Weigh 0.001 mol of SnCl 2 , 0.001 mol of SbCl 3 , 0.0001 mol of CoCl 2 6H 2 O and 0.032 mol of C 6 H 5 Na 3 O 7 2H 2 O, and dissolve them completely in 100 mL of deionized water to obtain a mixed salt solution. 0.05 g of graphite oxide was ultrasonically dispersed in the mixed salt solution, wherein the ultrasonic power was 100W.
(2)用NaOH调节0.1mol/L的NaBH4水溶液，使其pH≥12；将pH≥12的0.1mol/L的NaBH4水溶液缓慢滴加至步骤(1)中的混合盐溶液中并持续搅拌；滴加结束后，将混合溶液在80℃下加热5h。其中NaBH4水溶液的滴加速度为2mL/min，搅拌速度为800r/min。(2) Use NaOH to adjust the 0.1mol/L NaBH 4 aqueous solution to make its pH ≥ 12; slowly drop the 0.1 mol/L NaBH 4 aqueous solution with pH ≥ 12 into the mixed salt solution in step (1) and continue Stirring; after the dropwise addition, the mixed solution was heated at 80° C. for 5 h. Wherein the NaBH The rate of addition of the aqueous solution is 2mL/min, and the stirring speed is 800r/min.
(3)将混合溶液真空抽滤，并将抽滤得到沉淀物依次用去离子水、无水乙醇多次洗涤后进行真空干燥，得到SnSbCo/石墨烯前驱体粉末；然后将前驱体粉末置于管式炉中，在氩气保护条件下，300℃恒温煅烧4h，得到SnSbCo/石墨烯负极材料。其中，管式炉的升温速率为2℃/min。(3) The mixed solution is vacuum-filtered, and the precipitate obtained by the suction filtration is washed with deionized water and absolute ethanol several times and then vacuum-dried to obtain the SnSbCo/graphene precursor powder; then the precursor powder is placed in In a tube furnace, the SnSbCo/graphene negative electrode material was obtained by calcining at a constant temperature of 300 ° C for 4 h under the protection of argon. Wherein, the heating rate of the tube furnace is 2° C./min.
一种使用对比实施例制备的SnSbCo/石墨烯负极材料制备的钠离子电池。具体的，将SnSbCo/石墨烯材料、导电炭黑、粘结剂按照质量比为5:3:2混合均匀后，在铜箔上涂覆成均匀薄层，在真空80℃下干燥12h，辊压后切成圆形电极片。将圆形电极片、金属钠片、1mol/L的NaClO4/EC/DEC电解液组装成钠离子电池。在本实施例中，所述粘结剂为CMC粘结剂，所述薄层辊压后的厚度为70μm，所述圆形电极片的直径为18mm。A sodium ion battery prepared using the SnSbCo/graphene negative electrode material prepared in the comparative example. Specifically, after mixing the SnSbCo/graphene material, conductive carbon black, and binder uniformly according to the mass ratio of 5:3:2, they are coated on a copper foil to form a uniform thin layer, dried at 80°C for 12 hours in a vacuum, and rolled Cut into circular electrode sheets after pressing. A sodium-ion battery is assembled by a circular electrode sheet, a metal sodium sheet, and 1mol/L NaClO 4 /EC/DEC electrolyte. In this embodiment, the adhesive is a CMC adhesive, the thickness of the thin layer after rolling is 70 μm, and the diameter of the circular electrode sheet is 18 mm.
效果测试对比Effect test comparison
请参阅图1和图4，其分别是实施例1和对比实施例所制备的SnSbCo/石墨烯复合负极材料的XRD图谱。实施例1制备的SnSbCo/石墨烯复合负极材料的XRD图谱在接近23°衍射角的位置存在石墨烯的衍射峰，并且同时存在Sn-Sb、Co-Sb和Co-Sn合金相。而对比实施例制备的SnSbCo/石墨烯负极材料的XRD图谱中不存在氧化石墨的衍射峰，表面NaBH4能够充分还原氧化石墨。SnSbCo/石墨烯复合负极材料中的主要的合金相Sn-Sb的衍射峰的位置与JCPDS标准卡片(33-0118)相吻合，同时存在Co-Sb和Co-Sn合金相。Please refer to FIG. 1 and FIG. 4 , which are the XRD patterns of the SnSbCo/graphene composite negative electrode materials prepared in Example 1 and Comparative Example, respectively. The XRD pattern of the SnSbCo/graphene composite anode material prepared in Example 1 has a graphene diffraction peak at a position close to the 23° diffraction angle, and there are Sn-Sb, Co-Sb and Co-Sn alloy phases at the same time. However, there is no diffraction peak of graphite oxide in the XRD spectrum of the SnSbCo/graphene negative electrode material prepared in Comparative Example, and the surface NaBH 4 can fully reduce graphite oxide. The position of the diffraction peak of the main alloy phase Sn-Sb in the SnSbCo/graphene composite negative electrode material is consistent with the JCPDS standard card (33-0118), and there are Co-Sb and Co-Sn alloy phases at the same time.
请同时参阅图2-3和5-6，其分别是实施例1和对比实施例所制备的SnSbCo/石墨烯复合负极材料的SEM和TEM图。从图2和图3中可知，实施例1制备的SnSbCo/石墨烯复合负极材料中的石墨烯含量较多，能够很好的包裹合金颗粒，有效减少合金颗粒的团聚。而从图5和图6可知，对比实施例所制备的SnSbCo/石墨烯复合负极材料中，石墨烯含量少，合金颗粒团聚现象严重，不能有效嵌入石墨烯片层。Please also refer to Figures 2-3 and 5-6, which are the SEM and TEM images of the SnSbCo/graphene composite negative electrode materials prepared in Example 1 and Comparative Example, respectively. It can be seen from Figure 2 and Figure 3 that the graphene content in the SnSbCo/graphene composite negative electrode material prepared in Example 1 is relatively large, which can well wrap the alloy particles and effectively reduce the agglomeration of alloy particles. From Fig. 5 and Fig. 6, it can be seen that in the SnSbCo/graphene composite negative electrode material prepared in the comparative example, the graphene content is small, the alloy particle agglomeration phenomenon is serious, and the graphene sheet cannot be effectively embedded.
采用实施例1所制备的SnSbCo/石墨烯复合负极材料组装的钠离子电池为模拟电池1，采用对比实施例所制备的SnSbCo/石墨烯复合负极材料组装的钠离子电池为模拟电池2。The sodium-ion battery assembled with the SnSbCo/graphene composite negative electrode material prepared in Example 1 is simulated battery 1, and the sodium-ion battery assembled with the SnSbCo/graphene composite negative electrode material prepared in Comparative Example is simulated battery 2.
将制备得到的模拟电池1和模拟电池2分别进行恒流充放电测试，测试条件为：电流密度是100mA/g；电压是0-2.5V。图7和图8分别是模拟电池1和模拟电池2的充放电循环性能图。由图7可知，模拟电池1在100mA/g的电流密度下，首次放电比容量是998mAh/g，循环30次比容量可保持在600mAh/g，表现出较高的比容量及良好的循环性能。而由图8可知，模拟电池2在100mA/g的电流密度下，首次放电比容量为677mAh/g，循环30次后比容量降为464mAh/g，容量较低并且衰减趋势明显。The prepared simulated battery 1 and simulated battery 2 were respectively subjected to a constant current charge and discharge test under the following test conditions: the current density was 100mA/g; the voltage was 0-2.5V. 7 and 8 are charge-discharge cycle performance diagrams of simulated battery 1 and simulated battery 2, respectively. It can be seen from Figure 7 that under the current density of 100mA/g, the first discharge specific capacity of simulated battery 1 is 998mAh/g, and the specific capacity can be maintained at 600mAh/g after 30 cycles, showing a high specific capacity and good cycle performance . It can be seen from Figure 8 that the specific capacity of simulated battery 2 is 677 mAh/g for the first discharge at a current density of 100 mA/g, and the specific capacity drops to 464 mAh/g after 30 cycles, the capacity is low and the attenuation trend is obvious.
模拟电池2的充放电性能比模拟电池1差的主要原因为模拟电池2采用的对比实施例制备的SnSbCo/石墨烯复合负极材料，石墨烯含量少，合金颗粒团聚现象严重，不能有效嵌入石墨烯片层。The main reason why the charging and discharging performance of simulated battery 2 is worse than that of simulated battery 1 is that the SnSbCo/graphene composite negative electrode material prepared by the comparative example used in simulated battery 2 has less graphene content, serious alloy particle agglomeration, and cannot effectively embed graphene. lamellae.
采用实施例2制备的SnSbCo/石墨烯复合负极材料，同样因加入液氮使材料内部稳固性增加，但由于氧化石墨的含量与实施例1相比减少，使其比容量有所提高但循环稳定性欠佳，但仍旧优于对比实施例中材料的性能。The SnSbCo/graphene composite negative electrode material prepared in Example 2 also increases the internal stability of the material due to the addition of liquid nitrogen, but because the content of graphite oxide is reduced compared with Example 1, the specific capacity is increased but the cycle is stable. performance is poor, but still better than the performance of the material in the comparative examples.
采用实施例3制备的SnSbCo/石墨烯复合负极材料，与实施例1相比，大量加入液氮进行冷淬，进一步促进石墨烯更加牢固地包裹合金颗粒，能够有效减少不可逆容量，使后续充放电循环比容量有所提高。Using the SnSbCo/graphene composite negative electrode material prepared in Example 3, compared with Example 1, adding a large amount of liquid nitrogen for cooling can further promote graphene to wrap the alloy particles more firmly, which can effectively reduce the irreversible capacity and make the subsequent charge and discharge The cycle specific capacity has been improved.
相对于现有技术，本发明通过原位合成工艺，采用滴定还原法在制备石墨烯的同时形成纳米SnSbCo多元合金颗粒，有效提高材料制备效率。加入液氮急速冷却，通过冷淬工艺使片状石墨烯牢固的包裹SnSbCo合金颗粒，有效提高电极材料的结构稳定性。本发明制备得到的SnSbCo/石墨烯复合负极材料中的石墨烯含量较多，能够很好的包裹合金颗粒，有效减少合金颗粒的团聚，并且高导电率的石墨烯一方面可以提高电极材料的导电性，另一方面能够有效缓解合金颗粒在充放电过程中产生的体积膨胀。采用本发明的材料组装得到的钠离子电池具有高充放电比容量、良好的倍率性能和循环性能。Compared with the prior art, the present invention uses an in-situ synthesis process to form nano-SnSbCo multi-element alloy particles while preparing graphene by a titration reduction method, thereby effectively improving the material preparation efficiency. Liquid nitrogen is added for rapid cooling, and the sheet-like graphene is firmly wrapped around the SnSbCo alloy particles through the quenching process, which effectively improves the structural stability of the electrode material. The graphene content in the SnSbCo/graphene composite negative electrode material prepared by the present invention is relatively large, which can wrap the alloy particles well, effectively reduce the agglomeration of the alloy particles, and the graphene with high conductivity can improve the conductivity of the electrode material on the one hand. On the other hand, it can effectively alleviate the volume expansion of the alloy particles during the charging and discharging process. The sodium ion battery assembled by adopting the material of the invention has high charge-discharge specific capacity, good rate performance and cycle performance.
本发明并不局限于上述实施方式，如果对本发明的各种改动或变形不脱离本发明的精神和范围，倘若这些改动和变形属于本发明的权利要求和等同技术范围之内，则本发明也意图包含这些改动和变形。The present invention is not limited to the above-mentioned embodiments, if the various changes or deformations of the present invention do not depart from the spirit and scope of the present invention, if these changes and deformations belong to the claims of the present invention and the equivalent technical scope, then the present invention is also It is intended that such modifications and variations are included.
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