CN114551868B - 一种钠离子电池负极材料及其制备方法 - Google Patents
一种钠离子电池负极材料及其制备方法 Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 4
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 13
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- -1 copper fluoroborate Chemical compound 0.000 claims description 6
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 6
- 235000018417 cysteine Nutrition 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 4
- 239000005750 Copper hydroxide Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 claims description 3
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 claims description 3
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 3
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 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 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000011056 performance test Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- VJNMUKGZDONIAN-UHFFFAOYSA-N 1-methylisoquinolin-6-amine Chemical compound NC1=CC=C2C(C)=NC=CC2=C1 VJNMUKGZDONIAN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- QKDGGEBMABOMMW-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] QKDGGEBMABOMMW-UHFFFAOYSA-I 0.000 description 1
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 1
- IBJKCMMJJCJCLT-UHFFFAOYSA-M [S-2].[S-2].[SH-].[V+5] Chemical compound [S-2].[S-2].[SH-].[V+5] IBJKCMMJJCJCLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- HHQFLEDKAVLHOM-UHFFFAOYSA-N oxovanadium;trihydrofluoride Chemical compound F.F.F.[V]=O HHQFLEDKAVLHOM-UHFFFAOYSA-N 0.000 description 1
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AAWFOGYSSVYINI-UHFFFAOYSA-K triiodovanadium Chemical compound I[V](I)I AAWFOGYSSVYINI-UHFFFAOYSA-K 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- JTWLHYPUICYOLE-UHFFFAOYSA-J vanadium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[V+4] JTWLHYPUICYOLE-UHFFFAOYSA-J 0.000 description 1
- WSJLOGNSKRVGAD-UHFFFAOYSA-L vanadium(ii) bromide Chemical compound [V+2].[Br-].[Br-] WSJLOGNSKRVGAD-UHFFFAOYSA-L 0.000 description 1
- ZOYIPGHJSALYPY-UHFFFAOYSA-K vanadium(iii) bromide Chemical compound [V+3].[Br-].[Br-].[Br-] ZOYIPGHJSALYPY-UHFFFAOYSA-K 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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Abstract
本发明公开了一种钠离子电池负极材料,所述钠离子电池负极材料为球状Cu3VS4。本发明还公开一种钠离子电池负极材料的制备方法,将钒源、铜源与硫源加入到甲醇溶剂中于160~220℃温度下反应,且所述反应时达到钒源过量的环境,得到所述钠离子电池负极材料,所述钠离子电池负极材料为球状Cu3VS4。本发明负极材料在高电流密度下的具有优异的循环稳定性,同时制备方法简单,成本低。
Description
技术领域
本发明涉及一种电池负极材料及其制备方法,特别是一种钠离子电池负极材料及其制备方法。
背景技术
作为一种重要的储能器件,锂离子电池由于其工作电压高、能量密度高、循环寿命长、自放电率低、无记忆效应、环保等优点备受关注。目前,随着新能源汽车行业的飞速发展,对于锂离子电池的需求量愈来愈大。然而,全球的锂资源比较匮乏,难以实现大规模应用。
与锂离子电池相比,钠离子电池中钠资源更加丰富,价格也更为便宜,并且钠离子与锂离子有相似的化学性质,因此,钠离子电池将可以取代锂离子电池成为下一代主要的储能器件。然而,钠离子电池在工作过程中由于离子半径较大,钠离子迁移较缓慢,影响着钠离子电池的电化学性能。其中,电极材料是钠离子电池的关键组成部分,电极材料性能的优劣将直接影响着钠离子电池的性能,因此,开发具有优异的电化学性能的电极材料显得尤为重要。
发明内容
针对上述现有技术缺陷,本发明的任务在于提供一种钠离子电池负极材料,目的是解决钠离子电池现有缺陷,特别是由于较大的钠离子半径,导致电极材料难以实现在高电流密度下的长期循环稳定性问题。本发明的另一任务在于提供一种钠离子电池负极材料的制备方法。
本发明技术方案如下:一种钠离子电池负极材料,所述钠离子电池负极材料为球状Cu3VS4。
进一步地,所述球状Cu3VS4的直径为1~2μm。
一种钠离子电池负极材料的制备方法,将钒源、铜源与硫源加入到甲醇溶剂中于160~220℃温度下反应,且所述反应时达到钒源过量的环境,得到所述钠离子电池负极材料,所述钠离子电池负极材料为球状Cu3VS4。
进一步地,所述钒源为乙酰丙酮钒、钒的氧化物、钒酸盐和含钒卤化物中的一种或多种。
进一步地,所述铜源为铜盐,所述铜盐为硫酸铜、氯化铜、硝酸铜、氢氧化铜、柠檬酸铜、氟硼酸铜、乙酸铜、碘酸铜、碳酸铜、丁酸铜、草酸铜、磷酸铜、高氯酸铜和四氟硼酸铜中的一种或多种。
进一步地,所述硫源为硫代乙酰胺、硫脲和半胱氨酸中的一种或多种。
进一步地,所述反应的时间为12~72小时。
进一步地,所述钒源和所述硫源的摩尔比为1:0.5~1:2,所述钒源和所述铜源的摩尔比为1:0.1~1:0.5。
本发明与现有技术相比的优点在于:
本发明的球状Cu3VS4负极材料具有极大的比表面积,并且有利于电解液的浸润,显著增加了电解液与电极表面的接触面积,提供了更多的反应活性位点,可以缓冲电极材料充放电过程中的体积变化,防止了Cu3VS4的团聚,有利于保证球状的结构完整性,从而提高球状Cu3VS4的循环性能稳定性。本发明的制备方法操作简单,步骤简易,制备成本低。
附图说明
图1为本发明实施例1的X-射线衍射图。
图2为本发明实施例1的扫描电镜图(低倍数)。
图3为本发明实施例1的扫描电镜图(高倍数)。
图4为本发明实施例1的半电池的循环性能图。
具体实施方式
下面结合实施例对本发明作进一步说明,但不作为对本发明的限定。
本发明的钠离子电池负极材料的制备方法,将铜源、硫源以及过量的钒源加入到甲醇溶剂中反应,其中钒源为乙酰丙酮钒、钒的氧化物、钒酸盐和含钒卤化物中的一种或多种,具体可以是乙酰丙酮钒、五氧化二钒、二钒酸钠、钒过氧酸、硫酸氧钒、正钒酸、偏钒酸铵、二氧化钒、二溴化钒、二氧氯钒、偏钒酸钠、氢氧化钒、三碘化钒、三氟化钒、三氟氧钒、三硫化三钒、三氯化钒、三氯氧钒、三溴化钒、三氧化二钒、四氟化钒、四氯化钒、五氟化钒、五硫化二钒中的一种或多种。铜源为硫酸铜、氯化铜、硝酸铜、氢氧化铜、柠檬酸铜、氟硼酸铜、乙酸铜、碘酸铜、碳酸铜、丁酸铜、草酸铜、磷酸铜、高氯酸铜和四氟硼酸铜中的一种或多种。硫源为硫代乙酰胺、硫脲和半胱氨酸中的一种或多种。
实施例1
准确称量1.4g乙酰丙酮钒、0.3g硫代乙酰胺和0.16g三水硝酸铜,加入到35mL甲醇中,磁力搅拌5min,转速为500r/min,然后转入到50mL反应釜中,在200℃下反应24h,洗涤、干燥,即得到球状结构Cu3VS4负极材料。
图1为本实施例所得产物的X-射线衍射图,所有的X射线粉末衍射峰均可指标为Cu3VS4。图2为本实施例所得产物的低倍扫描电镜照片,从中可以看出本实施例所得样品为球状结构(1-2μm)。图3为本实施例所得产物的高倍扫描电镜照片,从中可以看出本实施例所得样品的球状结构表面粗糙。图4实施例所得产物对钠片做半电池的循环曲线图,在20Ag-1的高电流密度下经过25000次循环依然有274mAh g-1的容量,容量保持率为87%,表现出了优异的循环稳定性。
实施例2
准确称量0.37g五氧化二钒、0.3g硫脲和0.05g氯化铜,加入到35mL甲醇中,磁力搅拌5min,,转速为500r/min,然后转入到50ml反应釜中,在200℃环境中反应24h。将收集样品静置洗涤三次,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有251mAh g-1的容量。
实施例3
准确称量1.4g乙酰丙酮钒、0.3g硫代乙酰胺和0.16g三水硝酸铜,加入到35mL甲醇中,磁力搅拌5min,转速为500r/min,然后转入到50mL反应釜中,在160℃下反应24h,洗涤、干燥,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有269mAh g-1的容量。
实施例4
准确称量1.4g乙酰丙酮钒、0.3g硫代乙酰胺和0.16g三水硝酸铜,加入到35mL甲醇中,磁力搅拌5min,转速为500r/min,然后转入到50mL反应釜中,在220℃下反应24h,洗涤、干燥,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有240mAh g-1的容量。
实施例5
准确称量1.4g乙酰丙酮钒、0.3g硫代乙酰胺和0.16g三水硝酸铜,加入到35mL甲醇中,磁力搅拌5min,转速为500r/min,然后转入到50mL反应釜中,在200℃下反应12h,洗涤、干燥,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有242mAh g-1的容量。
实施例6
准确称量1.4g乙酰丙酮钒、0.3g硫代乙酰胺和0.16g三水硝酸铜,加入到35mL甲醇中,磁力搅拌5min,转速为500r/min,然后转入到50mL反应釜中,在200℃下反应72h,洗涤、干燥,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有249mAh g-1的容量。
实施例7
准确称量1.4g乙酰丙酮钒、0.6g硫代乙酰胺和0.16g三水硝酸铜,加入到35mL甲醇中,磁力搅拌3min,转速为500r/min,然后转入到50ml反应釜中,在200℃环境中反应24h。将收集样品静置洗涤三次,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有252mAh g-1的容量。
实施例8
准确称量1.4g乙酰丙酮钒、0.15g硫代乙酰胺和0.16g三水硝酸铜,加入到35mL去离子水中,磁力搅拌10min,转速为300r/min,然后转入到50ml反应釜中,在200℃环境中反应24h。将收集样品静置洗涤三次,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过25000次循环依然有261mAh g-1的容量。
实施例9
准确称量1.4g乙酰丙酮钒、0.3g硫代乙酰胺和0.1g三水硝酸铜,加入到35mL去离子水中,磁力搅拌10min,转速为300r/min,然后转入到50ml反应釜中,在200℃环境中反应24h。将收集样品静置洗涤三次,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过25000次循环依然有266mAh g-1的容量。
实施例10
准确称量1.4g乙酰丙酮钒、0.3g硫代乙酰胺和0.5g三水硝酸铜,加入到35mL去离子水中,磁力搅拌10min,转速为300r/min,然后转入到50ml反应釜中,在200℃环境中反应24h。将收集样品静置洗涤三次,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过25000次循环依然有259mAh g-1的容量。
实施例11
准确称量0.33g二氧化钒、0.48g半胱氨酸和0.07g氢氧化铜,加入到35mL去离子水中,磁力搅拌10min,转速为300r/min,然后转入到50ml反应釜中,在200℃环境中反应24h。将收集样品静置洗涤三次,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有257mAh g-1的容量。
实施例12
准确称量1.16g三溴化钒、0.48g半胱氨酸和0.11g硫酸铜,加入到35mL去离子水中,磁力搅拌10min,转速为300r/min,然后转入到50ml反应釜中,在200℃环境中反应24h。将收集样品静置洗涤三次,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有264mAh g-1的容量。
实施例13
准确称量0.47g偏钒酸铵、0.48g半胱氨酸和0.11g硫酸铜,加入到35mL去离子水中,磁力搅拌10min,转速为300r/min,然后转入到50ml反应釜中,在200℃环境中反应24h。将收集样品静置洗涤三次,即得到球状结构Cu3VS4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下经过20000次循环依然有260mAh g-1的容量。
对比例1
准确称量0.635g单质铜、1.02g单质钒和1.12g硫粉,混合在一起,并在研钵中研磨。然后将混合物置于在真空度<10-4毫巴的石英管中密封。以100℃/h的升温速度,加热到600℃,并保温24小时它,然后加热至850℃保温5天即得到纯相CuV2S4负极材料。所得材料对钠片做半电池进行电化学性能测试,在20A g-1的高电流密度下可以达到230mAh g-1的容量。
Claims (5)
1.一种钠离子电池负极材料的制备方法,其特征在于,将钒源、铜源与硫源加入到甲醇溶剂中于160~220℃温度下反应,且所述反应时达到钒源过量的环境,得到所述钠离子电池负极材料,所述钠离子电池负极材料为球状Cu3VS4,所述球状Cu3VS4的直径为1~2µm,所述钒源和所述硫源的摩尔比为1:0.5~1:2,所述钒源和所述铜源的摩尔比为1:0.1~1:0.5。
2.根据权利要求1所述的钠离子电池负极材料的制备方法,其特征在于,所述钒源为乙酰丙酮钒、钒的氧化物、钒酸盐和含钒卤化物中的一种或多种。
3.根据权利要求1所述的钠离子电池负极材料的制备方法,其特征在于,所述铜源为铜盐,所述铜盐为硫酸铜、氯化铜、硝酸铜、氢氧化铜、柠檬酸铜、氟硼酸铜、乙酸铜、碘酸铜、碳酸铜、丁酸铜、草酸铜、磷酸铜、高氯酸铜和四氟硼酸铜中的一种或多种。
4.根据权利要求1所述的钠离子电池负极材料的制备方法,其特征在于,所述硫源为硫代乙酰胺、硫脲和半胱氨酸中的一种或多种。
5.根据权利要求1所述的钠离子电池负极材料的制备方法,其特征在于,所述反应的时间为12~72小时。
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