CN106953087B - 钴酸锌、钴酸锌/碳布柔性复合材料的制备方法及其应用 - Google Patents
钴酸锌、钴酸锌/碳布柔性复合材料的制备方法及其应用 Download PDFInfo
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- CN106953087B CN106953087B CN201710233292.7A CN201710233292A CN106953087B CN 106953087 B CN106953087 B CN 106953087B CN 201710233292 A CN201710233292 A CN 201710233292A CN 106953087 B CN106953087 B CN 106953087B
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- 239000011701 zinc Substances 0.000 title claims abstract description 123
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 119
- 239000010941 cobalt Substances 0.000 title claims abstract description 119
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 108
- 239000002253 acid Substances 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 239000004744 fabric Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000004070 electrodeposition Methods 0.000 claims abstract description 26
- 239000002585 base Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000013110 organic ligand Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000004793 Polystyrene Substances 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 239000004005 microsphere Substances 0.000 claims description 17
- 229920002223 polystyrene Polymers 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011975 tartaric acid Substances 0.000 claims description 9
- 235000002906 tartaric acid Nutrition 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000004146 energy storage Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 239000008151 electrolyte solution Substances 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 238000000151 deposition Methods 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 8
- 230000005518 electrochemistry Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 22
- 239000010931 gold Substances 0.000 description 22
- 229910052737 gold Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000010183 spectrum analysis Methods 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 8
- 238000003837 high-temperature calcination Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000002659 electrodeposit Substances 0.000 description 3
- 210000004508 polar body Anatomy 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- -1 cobalt zinc hydroxide hydrate Chemical compound 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- H01M4/362—Composites
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- 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
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- H—ELECTRICITY
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- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明公开了一种钴酸锌的制备方法:将锌源、钴源、有机配体和碱混合后,制成电解液;在电解液中,通入惰性保护气体并在导电基体表面进行电化学沉积反应,反应完成后即在导电基体表面得到钴酸锌。本发明还公开了一种钴酸锌/碳布柔性复合材料的制备方法:选择碳布作为导电基体,并对导电基体进行预处理;将锌源、钴源、有机配体和碱混合后,制成电解液;将预处理后的导电基体放入电解液中,通入惰性保护气体并在碳布表面进行电化学沉积反应,反应完成后,清洗,干燥,即得到钴酸锌/碳布柔性复合材料。本发明首次以一步电化学沉积制备钴酸锌材料,在锂离子电池、超级电容器、析氧反应催化剂等多领域具有极其广阔的应用前景。
Description
技术领域
本发明属于电化学材料领域,尤其涉及一种钴酸锌、钴酸锌/碳布柔性复合材料的制备方法。
背景技术
钴酸锌作为一种重要的功能材料,具有成本低、环境友好等特点,在锂离子电池、超级电容器、析氧反应催化剂等多领域具有极其广阔的应用前景;其在作为锂离子电池电极材料时,锌离子能够与锂离子进行合金化/脱合金化的反应,增加了锂离子电池负极的能量密度。
目前已有的报道中大多采用高温煅烧经水热法合成的锌钴化合物前驱体,来制备钴酸锌材料。如文献[J.Mater.Chem A,2014,2,5434-5440],通过高温煅烧锌钴乙醇酸盐来制备钴酸锌微球;文献[J.Mater.Chem A,2016,4,10014-10022],通过高温煅烧锌钴羟基碳酸盐来制备钴酸锌粉末,公开号为CN103545507 A的中国专利公开了一种通过高温煅烧锌钴前驱体制备多孔钴酸锌粉末的方法。这些方法通常需要经过长时间水热和高温煅烧步骤,制备时间长、对设备要求高,不利于工业化生产,其在用制得的钴酸锌材料制备锂离子电池或超级电容器的电极时,需要加入一定量的粘结剂和导电物,不但使制备流程复杂化,同时降低了电极的能量密度,并增加了界面电阻。此外,也有研究者尝试用电化学沉积方法制备钴酸锌,但是只得到了钴锌水合氢氧化物或羟基氧化物类前驱体,后续仍旧需要通过高温煅烧制备的前驱体才能得到钴酸锌。这是由于电沉积金属氧化物与电沉积金属或合金相比,对合成路线的设计、实验条件的控制要严格的多,较难通过一步电沉积反应得到目标金属氧化物。例如:文献[J.Phy.Chem.Lett.,2014,5,2370-2374]通过电沉积的方法合成了氢氧化钴和氧化锌的混合物前驱体,然后通过550℃的高温煅烧得到钴酸锌,文献[RSCAdv.,2015,5,79397-79404]报道了通过电沉积得到锌钴水合氢氧化物,然后通过500℃煅烧6小时得到钴酸锌。由此可见,在已报道的与电化学合成相关的方法中,始终没有避开高温煅烧的步骤,且制备时间较长、步骤复杂。至今并没有关于一步电化学沉积法制备钴酸锌的报道。因此,研究一种工艺流程短、对设备要求低、利于工业化生产的钴酸锌制备方法,如:一步电化学沉积法是非常有必要的。
发明内容
本发明所要解决的技术问题是,克服以上背景技术中提到的不足和缺陷,提供一种工艺流程短、对设备要求低、利于工业化生产的钴酸锌以及具有高容量、高功率和高循环性能的钴酸锌/碳布柔性复合材料的制备方法。
为解决上述技术问题,本发明提出的技术方案为:
一种钴酸锌的制备方法,包括以下步骤:
(1)将锌源、钴源、有机配体和碱混合后,制成电解液;
(2)在所述电解液中,通入惰性保护气体并在导电基体表面进行电化学沉积反应,反应完成后即在所述导电基体表面得到钴酸锌,所述钴酸锌材料的分子式为ZnxCo3-xO4,其中0<x≤1;所述导电基体为金或不锈钢。
作为一个总的发明构思,本发明还提供一种钴酸锌/碳布柔性复合材料的制备方法,包括以下步骤:
(1)选择碳布作为导电基体,并对导电基体进行预处理;所述预处理过程是指将导电基体用蒸馏水、乙醇、丙酮反复清洗多次后,干燥得到预处理的导电基体;所述碳布的型号为W0S1002,CeTech Co,Taichung,Taiwan;
(2)将锌源、钴源、有机配体和碱混合后,制成电解液;
(3)将预处理后的碳布放入所述电解液中,通入惰性保护气体并在碳布表面进行电化学沉积反应,反应完成后,清洗,干燥,即得到所述钴酸锌/碳布柔性复合材料;所述钴酸锌材料的分子式为ZnxCo3-xO4,其中0<x≤1。
上述的制备方法,优选的,在所述的电解液中加入聚苯乙烯/丙烯酸微球再进行电化学沉积反应。
本发明的发明人发现,在电解液中加入带有阴离子基团的聚苯乙烯/丙烯酸微球可以作为形貌控制模板,可有效地改善电沉积得到的钴酸锌的表面形貌,增大钴酸锌的比表面积,从而提高其相关的电化学性能。
上述的制备方法,优选的,所述聚苯乙烯/丙烯酸微球的直径为10~1000nm;每升电解液中聚苯乙烯/丙烯酸微球的加入量为0.1~0.4g。所述聚苯乙烯/丙烯酸微球中丙烯酸和苯乙烯共聚体积比为1:1~100,进一步优选为1:9。进一步优选的,所述聚苯乙烯/丙烯酸微球的球径为100~300nm。
上述的制备方法,优选的,所述钴源选自硝酸钴、乙酸钴、氯化钴、硫酸钴、草酸钴中的至少一种;所述钴源选自硝酸锌、乙酸锌、氯化锌、硫酸锌、草酸锌中的至少一种;所述有机配体选自乙二胺四乙酸(EDTA)、乙酸、草酸、乳酸、酒石酸、乙二胺和三乙醇氨(TEA)中的至少一种;所述碱选自氢氧化钠、氢氧化钾、氢氧化锂、NH3中的至少一种。进一步优选的,所选有机配体为酒石酸、TEA、乙二胺四乙酸(EDTA)中的至少一种。
上述的制备方法,优选的,所述电解液中钴离子和锌离子的摩尔比为1:(1~100);进一步优选的,所述电解液中钴离子和锌离子的摩尔比为1:(1~30);所述钴源的浓度为2~10mmol;所述有机配体的浓度为20~40mmol。进一步优选的,所述电解液中锌离子和钴离子的摩尔比为1:(2~20)。
上述的制备方法,优选的,所述电解液的pH值不低于9。
上述的制备方法,优选的,所述电化学沉积过程中,反应的温度为50~105℃,反应电流密度不超过1A/cm2。进一步优选的,电流密度为0.0001~0.01A/cm2。
作为一个总的发明构思,本发明还提供一种由上述的制备方法获得的钴酸锌/碳布柔性复合材料在电化学储能器件上的应用。所述电化学储能器件为锂离子电池、钠离子电池、超级电容器中的一种或几种。
本发明利用有机配体、二价钴离子、氢氧根离子和二价锌离子的络合作用形成稳定的电解液,并在电解液中添加聚苯乙烯/丙烯酸微球,聚苯乙烯/丙烯酸微球由于其表面带有阴离子羧酸基团,电解液中的阳离子(二价锌离子和二价钴离子)会被快速地吸附到聚苯乙烯/丙烯酸微球表面,在导电基体表面施加一定电流时,吸附在聚苯乙烯/丙烯酸微球表面的钴、锌离子会与导电基底的接触点发生电化学氧化,二价钴离子由于氧化成三价后,与配体的络合能力减弱,从而形成尖晶石型钴氧化物,其中三价钴原子占据八面体位置,二价锌离子占据四面体位置,从而形成高比表面积的钴酸锌。
与现有技术相比,本发明的优点在于:
(1)本发明首次以一步电化学沉积制备钴酸锌材料,在锂离子电池、超级电容器、析氧反应催化剂等多领域具有极其广阔的应用前景。
(2)本发明采用电化学沉积法制备钴酸锌/碳布作为电极材料,库伦效率高、反应时间短、成本低、无需粘结剂、制备快速、高效高产、条件简单、步骤精简,有利于实现工业化生产。
(3)将本发明制备的钴酸锌/碳布作为电化学储能器件电极,其高比表面积有利于增大电极与电解液的接触,有利于离子的高效、快速扩散传输,在充放电过程中还能有效应对相变产生的体积膨胀,是优良的电化学储能器件电极材料,首次放电比容量高达2274.19mAh.g-1,具有高容量、高功率和高循环性能等优点。
附图说明
图1是本发明实施例1在不锈钢表面制备的钴酸锌的X射线衍射图。
图2是本发明实施例1在不锈钢表面制备的钴酸锌的扫描电镜图。
图3是本发明实施例1在不锈钢表面制备的钴酸锌的X射线能谱分析图。
图4是本发明实施例2在金片表面制备的钴酸锌的X射线衍射图。
图5是本发明实施例2在金片表面制备的钴酸锌的扫描电镜图。
图6是本发明实施例2在金片表面制备的钴酸锌的X射线能谱分析图。
图7是本发明实施例3制备的钴酸锌/碳布柔性复合材料的X射线衍射图。
图8是本发明实施例3制备的钴酸锌/碳布柔性复合材料的扫描电镜图。
图9是本发明实施例3制备的钴酸锌/碳布柔性复合材料的X射线能谱分析图。
图10是本发明实施例3制备的酸锌/碳布柔性复合材料制成电池的充放电曲线图。
图11是本发明实施例4制备的钴酸锌/碳布柔性复合材料的X射线衍射图。
图12是本发明实施例4制备的钴酸锌/碳布柔性复合材料的扫描电镜图。
图13是本发明实施例4制备的钴酸锌/碳布柔性复合材料的X射线能谱分析图。
图14是本发明实施例3和4制备的钴酸锌/碳布柔性复合材料制成电池的充放电曲线对比图。
图15是本发明实施例5制备的钴酸锌材料的扫描电镜图。
图16是本发明实施例5制备的钴酸锌材料的X射线能谱分析图。
图17是本发明实施例6制备的钴酸锌材料的扫描电镜图。
图18是本发明实施例6制备的钴酸锌材料的X射线能谱分析图。
具体实施方式
为了便于理解本发明,下文将结合说明书附图和较佳的实施例对本文发明做更全面、细致地描述,但本发明的保护范围并不限于以下具体实施例。
除非另有定义,下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的,并不是旨在限制本发明的保护范围。
除非另有特别说明,本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
实施例1:
一种本发明的钴酸锌的制备方法,包括以下步骤:
(1)将不锈钢片作为电沉积基体,分别用去离子水、乙醇、丙酮分别对其进行三次超声清洗,每次15分钟,最后用去离子水洗净并干燥待用;
(2)配制混合电解液100mL,其中硝酸钴浓度为5mmol/L,硝酸锌浓度为50mmol/L,酒石酸浓度为30mmol/L,氢氧化钠浓度为2mol/L;
(3)往步骤(2)中配制好的电解液中通入惰性保护气体至饱和,在97℃的温度下,并对电解液进行搅拌,放入步骤(1)后的不锈钢片,进行电化学沉积反应,反应过程中采用三电极体系,工作电极为不锈钢片,对电极为铂网,参比电极为银/氯化银电极,在0.0005A/cm2的电流密度下,进行恒电流沉积10分钟后,取出不锈钢片,不锈钢片上得到黑色沉积物,该黑色沉积物的X射线衍射图如图1所示,其显示该材料为尖晶石结构钴酸锌(Zn0.6Co2。 4O4)。
本实施例制备的钴酸锌材料的扫描电镜图如图2所示,显示钴酸锌能够均匀地沉积到不锈钢片表面,本实施例制备的钴酸锌材料的X射线能谱分析图如图3所示,表明该材料的锌含量占锌钴总含量的18.82%。
实施例2:
一种本发明的钴酸锌的制备方法,包括以下步骤:
(1)将金片作为电沉积基体,分别用去离子水、乙醇、丙酮分别对其进行三次超声清洗,每次15分钟,最后用去离子水洗净并干燥待用;
(2)配制混合电解液100mL,其中硝酸钴浓度为5mmol/L,硝酸锌浓度为50mmol/L,酒石酸浓度为30mmol/L,氢氧化锂浓度为2mol/L;
(3)往步骤(2)中配制好的电解液中通入惰性保护气体至饱和,在97℃的温度下,并对电解液进行搅拌,放入步骤(1)后的金片,进行电化学沉积反应,反应过程中采用三电极体系,工作电极为金片,对电极为铂网,参比电极为银/氯化银电极,在0.0005A/cm2的电流密度下,进行恒电流沉积10分钟后,取出金片,金片上得到黑色沉积物,该黑色沉积物的X射线衍射图如图4所示,其显示该材料为尖晶石结构钴酸锌(Zn0.47Co2.53O4)。
本实施例制备的钴酸锌材料的扫描电镜图如图5所示,显示钴酸锌能够均匀地沉积到金片表面,本实施例制备的钴酸锌材料的X射线能谱分析图如图6所示,表明该材料的锌含量占锌钴总含量的15.91%。
实施例3:
一种钴酸锌/碳布柔性复合材料的制备方法,包括以下步骤:
(1)选择柔性碳布(型号为W0S1002)作为导电基体,分别用去离子水、乙醇、丙酮分别对其进行三次超声清洗,每次15分钟,最后用去离子水洗净并干燥,得到预处理的导电基体;
(2)配制混合电解液100mL,其中乙酸钴浓度为5mmol/L,乙酸锌浓度为50mmol/L,酒石酸浓度为30mmol/L,氢氧化钠浓度为2mol/L;
(3)往步骤(2)中配制好的电解液中通入惰性保护气体至饱和,在97℃的温度下,并对电解液进行搅拌,放入步骤(1)后预处理的导电基体,进行电化学沉积反应,反应过程中采用三电极体系,工作电极为柔性碳布,对电极为铂网,参比电极为银/氯化银电极,在0.5mA/cm2的电流密度下,进行恒电流沉积10分钟后,取出柔性碳布,用去离子水冲洗干净后干燥,即得到钴酸锌/碳布柔性复合材料。
本实施例制备钴酸锌/碳布柔性复合材料的X射线衍射图如图7所示,显示在碳材料表面的物质为尖晶石结构钴酸锌(Zn0.7Co2.3O4);本实施例制备钴酸锌/碳布柔性复合材料的扫描电镜图如图8所示,本实施例制备的钴酸锌材料的X射线能谱分析图如图9所示,表明该材料的锌含量占锌钴总含量的23.33%。
以本实例制备的钴酸锌/碳布柔性复合材料作为工作电极、锂片为对电极装配的扣式电池的充放电曲线如图10所示,由图10可知本实例制备的钴酸锌/碳布柔性复合材料显示出较高的比容量,在0.2A.g-1的电流密度下,0.01~3V的电压窗口内,首次放电比容量达到956.10mAh.g-1,首次放电容量达到803.53mAh.g-1,相比于石墨碳型负极材料(比容量约为370mAh.g-1),适合作为锂离子电池电极材料。
实施例4:
一种钴酸锌/碳布柔性复合材料的制备方法,包括以下步骤:
(1)选择柔性碳布(型号为W0S1002)作为导电基体,分别用去离子水、乙醇、丙酮分别对其进行三次超声清洗,每次15分钟,最后用去离子水洗净并干燥,得到预处理的导电基体;
(2)配制混合电解液100mL,其中硝酸钴浓度为5mmol/L,硝酸锌浓度为50mmol/L,酒石酸浓度为30mmol/L,氢氧化钠浓度为2mol/L,聚苯乙烯/丙烯酸微球浓度为0.4g/L(苯乙烯和丙烯酸共聚体积比为9:1);
(3)往步骤(2)中配制好的电解液中通入惰性保护气体至饱和,在97℃的温度下,并对电解液进行搅拌,放入步骤(1)后预处理的导电基体,进行电化学沉积反应,反应过程中采用三电极体系,工作电极为柔性碳布,对电极为铂网,参比电极为银/氯化银电极,在0.5mA/cm2的电流密度下,进行恒电流沉积10分钟后,取出柔性碳布,浸泡在二甲亚砜溶液中,持续溶解聚苯乙烯/丙烯酸微球12小时后,用去离子水冲洗干净后干燥,即得到钴酸锌(Zn0.75Co2.25O4)/碳布柔性复合材料。
本实施例制备钴酸锌/碳布柔性复合材料的X射线衍射图如图11所示,钴酸锌/碳布柔性复合材料的扫描电镜图如图12所示,其显示添加聚苯乙烯/丙烯酸微球而电沉积得到的钴酸锌呈微纳柱状结构,形貌得到明显改善,其比表面积明显大于实施例3中的钴酸锌。本实施例制备的钴酸锌材料的X射线能谱分析图如图13所示,表明该材料的锌含量占锌钴总含量的24.87%。
图14为本实施例和实施例3制备的钴酸锌/碳布柔性复合材料制成电池的充放电曲线比较图,在0.2A.g-1的电流密度下,0.01~3V的电压窗口内,其显示本实施例的钴酸锌/碳布柔性复合材料制成电池首次放电比容量高达2274.19mAh.g-1,首次充电比容量高达1945.21mAh.g-1,可见添加聚苯乙烯/丙烯酸微球之后,钴酸锌/碳布柔性电极的能量密度进一步提高,适合作为锂离子电池负极的应用。
实施例5:
一种本发明的钴酸锌的制备方法,包括以下步骤:
(1)将金片作为电沉积基体,分别用去离子水、乙醇、丙酮分别对其进行三次超声清洗,每次15分钟,最后用去离子水洗净并干燥待用;
(2)配制混合电解液100mL,其中硝酸钴浓度为5mmol/L,硝酸锌浓度为10mmol/L,酒石酸浓度为30mmol/L,氢氧化锂浓度为2mol/L;
(3)往步骤(2)中配制好的电解液中通入惰性保护气体至饱和,在97℃的温度下,并对电解液进行搅拌,放入步骤(1)后的金片,进行电化学沉积反应,反应过程中采用三电极体系,工作电极为金片,对电极为铂网,参比电极为银/氯化银电极,在0.0005A/cm2的电流密度下,进行恒电流沉积10分钟后,取出金片,金片上得到黑色沉积物,该材料为尖晶石结构钴酸锌(Zn0.2Co2.8O4)。
本实施例制备的钴酸锌材料的扫描电镜图如图15所示,显示钴酸锌能够均匀地沉积到金片表面。本实施例制备的钴酸锌材料的X射线能谱分析图如图16所示,表明该材料的锌含量占锌钴总含量的6.69%
实施例6:
一种本发明的钴酸锌的制备方法,包括以下步骤:
(1)将金片作为电沉积基体,分别用去离子水、乙醇、丙酮分别对其进行三次超声清洗,每次15分钟,最后用去离子水洗净并干燥待用;
(2)配制混合电解液100mL,其中硝酸钴浓度为5mmol/L,硝酸锌浓度为100mmol/L,酒石酸浓度为30mmol/L,氢氧化锂浓度为2mol/L;
(3)往步骤(2)中配制好的电解液中通入惰性保护气体至饱和,在97℃的温度下,并对电解液进行搅拌,放入步骤(1)后的金片,进行电化学沉积反应,反应过程中采用三电极体系,工作电极为金片,对电极为铂网,参比电极为银/氯化银电极,在0.0005A/cm2的电流密度下,进行恒电流沉积10分钟后,取出金片,金片上得到黑色沉积物,该材料为尖晶石结构钴酸锌(Zn0.83Co2.17O4)。
本实施例制备的钴酸锌材料的扫描电镜图如图17所示,显示钴酸锌能够均匀地沉积到金片表面。本实施例制备的钴酸锌材料的X射线能谱分析图如图18所示,表明该材料的锌含量占锌钴总含量的27.78%。
从实施例2、实施例5和实施例6的得到的钴酸锌的锌钴元素比可以看出,通过控制锌离子在电解液中的浓度,可以有效控制钴酸锌的锌含量增减。
Claims (8)
1.一种钴酸锌的制备方法,其特征在于,包括以下步骤:
(1)将锌源、钴源、有机配体和碱混合后,制成电解液;
(2)在所述电解液中,通入惰性保护气体并在导电基体表面进行电化学沉积反应,反应完成后即在所述导电基体表面得到钴酸锌;在所述的电解液中加入聚苯乙烯/丙烯酸微球再进行电化学沉积反应。
2.一种钴酸锌/碳布柔性复合材料的制备方法,其特征在于,包括以下步骤:
(1)选择碳布作为导电基体,并对导电基体进行预处理;
(2)将锌源、钴源、有机配体和碱混合后,制成电解液;
(3)将预处理后的导电基体放入所述电解液中,通入惰性保护气体并在碳布表面进行电化学沉积反应,反应完成后,清洗,干燥,即得到所述钴酸锌/碳布柔性复合材料;在所述的电解液中加入聚苯乙烯/丙烯酸微球再进行电化学沉积反应。
3.如权利要求1或2所 述的制备方法,其特征在于,所述聚苯乙烯/丙烯酸微球的直径为10~1000nm;每升电解液中聚苯乙烯/丙烯酸微球的加入量为0.1~0.4g。
4.如权利要求1或2所述的制备方法,其特征在于,所述钴源选自硝酸钴、乙酸钴、氯化钴、硫酸钴、草酸钴中的至少一种;所述钴源选自硝酸锌、乙酸锌、氯化锌、硫酸锌、草酸锌中的至少一种;所述有机配体选自乙二胺四乙酸、乙酸、草酸、乳酸、酒石酸、乙二胺和三乙醇氨中的至少一种;所述碱选自氢氧化钠、氢氧化钾、氢氧化锂、NH3中的至少一种。
5.如权利要求1或2所述的制备方法,其特征在于,所述电解液中钴离子和锌离子的摩尔比为1:(1~100),钴源的浓度为2~10mmol/L,有机配体的浓度为20~40mmol/L。
6.如权利要求1或2所述的制备方法,其特征在于,所述电解液的pH值不低于9。
7.如权利要求1或2所述的制备方法,其特征在于,所述电化学沉积过程中,反应的温度为50~105℃,反应电流密度不超过1A/cm2。
8.一种如权利要求2~7任一项所述的制备方法获得的钴酸锌/碳布柔性复合材料在电化学储能器件上的应用。
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