CN115744979B - Method for preparing carbon nano tube composite potassium vanadate in situ and application of carbon nano tube composite potassium vanadate in metal ion battery - Google Patents
Method for preparing carbon nano tube composite potassium vanadate in situ and application of carbon nano tube composite potassium vanadate in metal ion battery Download PDFInfo
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- CN115744979B CN115744979B CN202111029397.3A CN202111029397A CN115744979B CN 115744979 B CN115744979 B CN 115744979B CN 202111029397 A CN202111029397 A CN 202111029397A CN 115744979 B CN115744979 B CN 115744979B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 49
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 47
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title abstract description 22
- 239000002131 composite material Substances 0.000 title abstract description 14
- 238000011065 in-situ storage Methods 0.000 title abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 36
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 28
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 24
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 239000002127 nanobelt Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229960003975 potassium Drugs 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 239000010405 anode material Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 2
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 229940093928 potassium nitrate Drugs 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 229940093914 potassium sulfate Drugs 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 239000012002 vanadium phosphate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 10
- 238000009831 deintercalation Methods 0.000 abstract description 6
- 239000001103 potassium chloride Substances 0.000 abstract description 6
- 235000011164 potassium chloride Nutrition 0.000 abstract description 6
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000002074 nanoribbon Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 43
- 238000012360 testing method Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 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 5
- 230000008901 benefit Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002079 double walled nanotube Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 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
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of metal ion battery positive electrode materials, and particularly relates to a method for in-situ synthesis of a one-dimensional carbon nanotube composite potassium vanadate nanobelt positive electrode material and application of the positive electrode material in a metal ion battery, wherein the positive electrode material has a chemical formula of KV (kilovolt) 3 O 8 @CNTs. KV of the invention 3 O 8 The @ CNTs are prepared by ball milling a vanadium precursor, sequentially adding potassium chloride, carbon nanotubes and a reducing agent, stirring at room temperature, performing ultrasonic treatment and performing hydrothermal synthesis. In the obtained product, potassium vanadate with a nano-ribbon structure and one-dimensional carbon nanotubes grow into a cross-linked three-dimensional network structure in situ, and the specific discharge capacity of the material is greatly improved; in addition, the transmission path of sodium ions in the solid phase is shortened, which is favorable for rapid deintercalation of sodium ions; meanwhile, the introduced carbon nano tube provides a good conductive network for electron transfer, is beneficial to improving the electron conduction rate and improves the charge and discharge of the batteryReaction kinetics in electrical processes.
Description
Technical Field
The invention belongs to the field of metal ion battery anode materials, and particularly relates to a method for preparing carbon nano tube composite potassium vanadate in situ and application thereof.
Background
Along with the proposal of the peak reaching and the neutralization targets of carbon in China, new energy sources become the main bodies of power supply. However, the clean renewable energy source represented by wind energy and solar energy has the defects of randomness, intermittence and uncontrollable, so that the clean renewable energy source cannot be directly integrated into a power grid for use, otherwise, the output quality of power consumption is affected, and the safety problem of a power system is accompanied, so that the safe and stable operation of the power grid is affected, and meanwhile, the problem also causes the waste of a large amount of renewable energy source output power. The development of the energy storage technology is a key for solving the problems of discontinuity, instability, wind and light discarding and the like, and is a key for supporting the large-scale development of new energy in China, ensuring the safety of the new energy and promoting the practicability of the new energy. Among the existing energy storage technologies, the development of the lithium ion battery energy storage technology is mature and perfect, and the lithium ion battery energy storage technology is widely applied to power batteries of various portable electronic devices and the like due to the advantages of high energy density, high power density, long cycle life and the like, but the large-scale development of the lithium ion battery is greatly limited due to the problems of limited lithium resource reserves, high price, uneven resource distribution and the like.
Sodium and lithium have similar physicochemical properties, and sodium is considered as an excellent candidate for replacing lithium ion batteries and realizing large-scale energy storage due to the advantages of richer reserves, wider distribution, lower cost and the like. The positive electrode is an important component of the sodium ion battery, and occupies about one third of the cost of the whole battery, and determines the output voltage, capacity and safety of the whole battery. From the current report, the research of the positive electrode material of the sodium ion battery mainly focuses on layered oxides, polyanion compounds, prussian blue compounds and organic compounds. Among the numerous sodium ion battery cathode materials, layered oxides are receiving extensive attention from researchers due to the advantages of high capacity, rich elements, flexible components, easy mass preparation, and the like. The vanadyl oxide is used as one of layered oxides, and is also a material for more research due to the good sodium deintercalation capability and higher theoretical specific capacity. However, the lower intrinsic conductivity greatly limits the specific capacity and the multiplying power performance, so that the large-scale preparation and the commercial popularization cannot be realized. The carbon coating is used as a common material modification mode, so that the effects of greatly improving the surface conductivity of the material, improving the wettability of electrolyte and reducing the interface charge transfer impedance can be realized, however, the structure of the material is easy to change at high temperature, the effective load of carbon on the material is difficult to realize by the existing synthesis process, and the practical application of the material is limited.
Disclosure of Invention
Aiming at the technical problems, the three-dimensional network structure formed by mutually connecting the one-dimensional carbon nano tube and the potassium vanadate nanobelt is constructed in situ by a low-temperature hydrothermal synthesis method. Meanwhile, unlike the traditional method of coating carbon materials such as carbon nano tubes by physical mixing, mechanical coating and the like, the composite material prepared in situ benefits from the effect of the carbon nano tubes as heterogeneous nucleation cores and the induction and dispersion effect of the carbon nano tubes on the growth of potassium vanadate nano bands, so that the nucleation rate of the prepared potassium vanadate in the process of nucleation is improved, the agglomeration phenomenon of the potassium vanadate nano bands is effectively avoided while the prepared potassium vanadate has uniform nano band morphology and size, the uniform crosslinking and growth of the potassium vanadate nano bands on the carbon nano tubes are realized, and the carbon nano tube composite potassium vanadate electrode material has good material stability in the process of de-intercalation by virtue of the excellent mechanical property of the carbon nano tubes; in addition, the three-dimensional interconnection network structure not only can be used as a continuous conductive path to provide more adsorption sites for the three-dimensional interconnection network structure, so that the battery has higher reactivity in the charge and discharge process, and the effective capacity of the material is greatly improved; meanwhile, due to the dispersion effect of the carbon nano tube, the agglomeration phenomenon of the potassium vanadate nano belt in the growth process is effectively avoided, so that the composite material with the reticular structure has a larger specific surface area, and the rate capability of the material is improved to a certain extent. The prepared vanadate has higher specific discharge capacity and excellent multiplying power performance in electrochemical performance test, and has good application prospects in energy storage and power batteries.
The invention relates to a method for preparing carbon nano tube composite potassium vanadate and application thereof in a metal ion battery. The technical scheme is as follows:
one aspect of the invention provides a metal ion battery positive electrode material, wherein the composition of the positive electrode material is KV 3 O 8 @CNTs; the positive electrode material is of a three-dimensional network structure formed by crosslinking a one-dimensional carbon nano tube and a potassium vanadate nano belt; the positive electrode material is a nanotube-supported material with a band diameter of 10-150nm, and the band diameter range of the positive electrode material is preferably 50-100nm.
The invention also provides a preparation method of the metal ion battery anode material, which comprises the following steps:
1) Weighing a proper amount of vanadium source, drying and ball milling; preferably, the vanadium source is placed in an oven at 60-120 ℃ to be dried for 6-12 hours, and the dried vanadium source is transferred to a ball milling tank to be ball milled for 4-8 hours at 300-600 r/min; further, the preferred temperature range is 80-100deg.C, and the preferred drying time is 8-10h; the ball milling speed is preferably 400-500r/min, and the ball milling time is preferably 6-7h.
2) Adding a vanadium source, a carbon source, a reducing agent and a potassium source after ball milling into a solvent to form a mixed solution, wherein the mass concentration of the solid content/solvent is 150-350mg/mL; the mol ratio of the vanadium to the reducing agent is 1:0.9-1.1; the molar ratio of vanadium to potassium is 1:3-5, the mass fraction of the carbon nano tube in the vanadium source is 5-20% (the carbon nano tube added in the preparation process is usually excessive, and the carbon nano tube in the actual composite materialRice Guan Zhan KV 3 O 8 The proportion of (2) is 5-8 wt%; preferably, the mass concentration of the solid content/solvent in the mixed solution is 200-300mg/mL; the molar ratio of the vanadium to the reducing agent is 1:1; the molar ratio of the vanadium source to the potassium source is 1:4, and the carbon nano tube accounts for 5-10% of the mass of the vanadium source.
3) Stirring the mixed solution obtained in the step 2) for 5-8 hours in a water bath at the temperature of 30-50 ℃ to fully react; then, carrying out ultrasonic dispersion for 6-12 hours to obtain a mixture precursor, and transferring the mixture precursor into a 100mL reaction kettle; wherein the water bath temperature is preferably 30-40 ℃, and the stirring time is preferably 6-7h; preferably, the ultrasonic dispersion is carried out for 8 to 10 hours.
4) Placing the reaction kettle obtained in the step 3) in an oven with the temperature of 120-180 ℃ for reaction for 12-48h, preferably 120-150 ℃, and preferably 24-36h.
5) Centrifuging the mixture after the reaction in the step 4) to obtain a precipitate, washing, drying, and grinding to obtain the carbon nano tube composite potassium vanadate anode material; preferably, deionized water and ethanol are used for cleaning for 2-5 times respectively in turn, and drying is carried out for 8-18 hours at the temperature of 80-160 ℃; further, the preferable times are 3-4 times and 2-3 times in sequence, the preferable drying temperature is 80-120 ℃, and the drying time is 8-16 hours, so that the metal ion battery anode material is obtained.
Preferably, the vanadium source is one or two or more of vanadium phosphate, ammonium metavanadate, vanadium pentoxide and vanadium trioxide, the carbon nanotubes are one or two or more of single-wall carbon nanotubes, multi-wall carbon nanotubes, double-wall carbon nanotubes or few-wall carbon nanotubes, and the reducing agent is one or two or more of citric acid, oxalic acid, ascorbic acid, polyethylene glycol and hydrogen peroxide; the potassium source is one or more of potassium hydroxide, potassium oxalate, potassium sulfate, potassium citrate, potassium nitrate, potassium fluoride, potassium bicarbonate and potassium carbonate; the solvent is one or more of deionized water, ultrapure water and distilled water.
In yet another aspect, the invention provides a metal ion battery positive electrode comprising the metal ion battery positive electrode material described above.
The invention also provides a metal ion battery, which comprises the metal ion battery anode.
Preferably, the metal ion battery is a sodium ion battery or an aqueous zinc ion battery.
Preferably, when the metal ion battery is a sodium ion battery, the battery composition is: the prepared KV 3 O 8 The @ CNTs positive electrode material is dissolved in NMP according to the proportion of active substance to conductive agent to binder=7:2:1 to prepare slurry, and then the slurry is used as the positive electrode of the sodium ion battery. The metal sodium sheet is used as a negative electrode, the glass fiber membrane is used as a diaphragm, and the solute is 1M NaClO 4 (sodium perchlorate), a mixture of solvents EC (ethylene carbonate) and DEC (diethyl carbonate) (mass ratio 1:1), wherein an additive is FEC with mass fraction of 2% as electrolyte, aluminum foil is used as a current collecting plate, and the CR2016 button type sodium ion battery is formed by sequentially stacking and compressing a negative electrode shell, a negative electrode, electrolyte, a diaphragm, electrolyte, a positive electrode and a current collector positive electrode shell according to the sequence.
Advantageous effects
(1) KV of the invention 3 O 8 The @ CNTs are prepared by a hydrothermal synthesis method, and the microstructure of the synthetic material is in a three-dimensional network structure, so that the synthetic material has a relatively high specific surface area. Meanwhile, the effective three-dimensional conductive network increases the conductivity of the material, is favorable for realizing rapid and stable intercalation and deintercalation of sodium ions in the electrode material, and the combination of the aspects ensures that the material shows good electrochemical performance, including good rate performance and specific discharge capacity. In conclusion, the material has potential application prospects in large-scale energy storage technology.
(2) The KV with the nano ribbon structure is prepared in situ by using a hydrothermal synthesis method 3 O 8 The carbon nano tube is used as a heterogeneous nucleation core and a dispersing agent in the growth process of potassium vanadate nucleation, so that the nucleation rate of potassium vanadate is effectively improved, and meanwhile, the interaction of induction and dispersion is exerted on potassium vanadate nucleation and growth, so that the agglomeration phenomenon of the potassium vanadate nanobelt caused by disordered growth is relieved, and the size distribution of the potassium vanadate nanobelt is uniform. In addition, potassium vanadate is used inThe carbon nano tube spontaneously nucleates and grows in situ on the basis of the self-assembled three-dimensional conductive network formed by the mutual crosslinking of the one-dimensional carbon nano tube and the potassium vanadate nano belt, the conductive network can be used as a continuous conductive path, a good conductive network is provided for electron transfer, the rapid conduction of electrons is facilitated, and the reaction kinetics in the charge and discharge processes of the battery is improved; the diameter of the potassium vanadate nanobelt is effectively controlled due to the introduction of the carbon nano tube, so that the overall shape of the material maintains high consistency, the transmission path of sodium ions in a solid phase is shortened, the mass transfer resistance is reduced, and sodium deintercalation is facilitated when the sodium ions enter a bulk phase lattice rapidly; in addition, unlike the carbon coated products prepared by the conventional processes of ball milling amorphous carbon coated, physical mixing carbon nano tube coated, hydrothermal amorphous carbon coated and the like, the electrode material effectively relieves the problems of agglomeration and the like caused by disordered growth of potassium vanadate due to the dispersion effect of the carbon nano tube, has higher specific surface area, ensures that the contact area of electrolyte and an electrode is larger in the charge and discharge process of the battery, provides more adsorption sites for sodium ions, greatly improves the reactivity of the battery, ensures that the material is more fully reacted, and greatly improves the effective capacity of the material; in summary, the present invention achieves an improvement in reaction kinetics from both electron transfer and ion diffusion, and a reduction in battery polarization, and therefore, a battery assembled therefrom has excellent rate performance and effective specific capacity.
Drawings
Fig. 1 is an SEM image of the positive electrode materials prepared in example 1, example 2, comparative example 1, comparative example 2, and comparative example 3.
Fig. 2 is an X-ray diffraction pattern of the positive electrode materials prepared in example 1, example 2, comparative example 1, comparative example 2, and comparative example 3.
Fig. 3 is a graph showing the rate performance of the positive electrode materials prepared in example 1, example 2, comparative example 1, comparative example 2, and comparative example 3 in sodium ion batteries.
Fig. 4 is a graph showing the cycle performance of the positive electrode materials prepared in example 1, example 2, comparative example 1, comparative example 2, and comparative example 3 in sodium ion batteries.
Fig. 5 is EIS spectra of the positive electrode materials prepared in example 1, example 2, comparative example 1, comparative example 2, comparative example 3 in sodium ion batteries.
Fig. 6 is a BET and pore distribution diagram of the positive electrode material prepared in example 1 and comparative example 1.
Fig. 7 is an electrochemical performance diagram of the positive electrode material prepared in example 1 in an aqueous zinc ion battery.
Fig. 8 is a graph showing the cycle performance of the positive electrode material prepared in example 1 in an aqueous zinc ion battery.
Detailed Description
The following is further described in conjunction with specific embodiments to enable one skilled in the art to more readily understand the advantages and features of the present invention. The starting materials used in the examples below are all commercially available conventional products.
Example 1
(V 2 O 3 Hydrothermal preparation of KV for precursor 3 O 8 @CNTs)
0.65g of commercial V is weighed after ball milling for 6 hours at the rotating speed of 400r/min 2 O 3 And 8.76g potassium chloride in a 100mL beaker, adding 60mL deionized water followed by 20mL hydrogen peroxide solution (30 wt%) and 0.1g carbon nanotubes (where carbon nanotubes are in excess, actual carbon nanotubes account for KV in the composite) 3 O 8 About 5 percent) and stirring for 6 hours at room temperature to obtain a black-green solution, and then carrying out ultrasonic treatment for 8 hours; transferring the mixture to a hydrothermal reaction kettle, placing the mixture in a 140 ℃ oven for reaction for 18 hours, taking out a sample in the reaction kettle after the mixture is cooled, respectively washing the sample with deionized water and ethanol for 3 times, centrifuging the sample, and placing the obtained gray green powder in a 120 ℃ vacuum drying oven for drying for 12 hours to obtain a final product KV 3 O 8 CNTs, characterized by SEM testing with a band diameter in the range of 50-100nm.
Example 2
(V 2 O 5 Hydrothermal preparation of KV for precursor 3 O 8 @CNTs)
0.85g of commercial V is weighed after ball milling for 6 hours at the rotating speed of 400r/min 2 O 5 And 8.76g of potassium chloride in a 100mL beaker, adding 60mL deionized water followed by 20mL of peroxideHydrogen solution (30 wt%) and 0.1g of carbon nano tube, stirring at room temperature for 6h to obtain orange-yellow solution, then ultrasonic-treating for 8h; transferring the mixture to a hydrothermal reaction kettle, placing the mixture in a 140 ℃ oven for reaction for 18 hours, taking out a sample in the reaction kettle after the mixture is cooled, respectively washing the sample with deionized water and ethanol for 3 times, centrifuging the sample, and drying the obtained tan powder in a 120 ℃ vacuum drying oven for 12 hours to obtain a final product KV 3 O 8 CNTs, characterized by SEM testing with a band diameter in the range of 50-100nm.
Comparative example 1
(V 2 O 3 Hydrothermal preparation of KV for precursor 3 O 8 )
0.65g of commercial V is weighed after ball milling for 6 hours at the rotating speed of 400r/min 2 O 3 And 8.76g of potassium chloride in a 100mL beaker, adding 60mL of deionized water, adding 20mL of hydrogen peroxide, stirring at room temperature for 2 hours to obtain a black-green solution, transferring the mixture to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a 140 ℃ oven for reaction for 18 hours, taking out a sample in the reaction kettle after the hydrothermal reaction kettle is cooled, respectively washing the sample for 3 times by using the deionized water and ethanol, centrifuging, and drying the obtained gray-green powder in a vacuum drying oven at 120 ℃ for 12 hours to obtain a final product KV 3 O 8 The band diameter range was characterized by SEM test to be 200-300nm.
Comparative example 2
(V 2 O 3 Ball milling method for preparing KV 3 O 8 @C)
Weighing 0.3747g V 2 O 3 And 14.91g of potassium chloride and adding 100mL of deionized water into a 200mL beaker, stirring at room temperature for 72h, centrifuging the obtained mixture, removing supernatant, respectively cleaning with deionized water and ethanol for 3 times, centrifuging, and drying the obtained gray black powder in a vacuum drying oven at 120 ℃ for 12h to obtain a product KV 3 O 8 Transferring 1g of the post-sampling product and 0.1g of ketjen black into a ball milling tank, and ball milling for 6 hours at a rotating speed of 400r/min to obtain carbon-coated KV 3 O 8 And @ C. The nanoribbon radius, which characterizes the ribbon structure by SEM testing, ranges from 200-300nm.
Comparative example 3
(V 2 O 3 Hydrothermal preparation of KV by taking @ C as precursor 3 O 8 @C)
0.5849g NH was weighed 4 VO 3 And 1.057g of citric acid monohydrate is added into a 500mL beaker, 400mL of deionized water is added, the mixture is heated in a water bath at 80 ℃ and stirred for 1h to obtain a black green solution, stirring is continued for 4h to obtain 30mL of gel, the obtained mixture is placed into a vacuum drying oven at 120 ℃ for drying for 12h, the obtained solid powder is subjected to pre-carbonization at 350 ℃ for 5h under argon atmosphere, sintering at 750 ℃ for 8h to obtain a precursor VOx@C of which the surface is coated with a carbon layer, 14.91g of potassium chloride is weighed and added with 100mL of deionized water, stirring is carried out at room temperature for 2h, the mixture is transferred to a hydrothermal reaction kettle, placed into an oven at 120 ℃ for reacting for 18h, a sample in the reaction kettle is taken out after the sample is cooled, the sample is respectively washed for 3 times by deionized water and ethanol and centrifuged, and the obtained gray black powder is placed into the vacuum drying oven at 120 ℃ for drying for 12h to obtain a final KV product 3 O 8 And @ C, characterized by SEM testing by a band diameter in the range of 200-300nm.
Analysis of experimental results:
the positive electrode materials prepared in examples 1-2 and comparative examples 1-3 were subjected to SEM characterization, and the results are shown in fig. 1. From fig. 1, it can be seen that the SEM image of the embodiment shows that the one-dimensional carbon nanotubes and the potassium vanadate nanobelts are crosslinked into a three-dimensional network structure, the embodiment can effectively control the uniformity of the diameters of the material nanobelts by compounding the potassium vanadate with the carbon nanotubes, and meanwhile, the embodiment forms the potassium vanadate nanobelts with the band diameter range within 100nm, so that the transmission path of sodium ions in a solid phase is shortened, the rapid deintercalation of sodium ions is facilitated, meanwhile, the SEM image has a larger specific surface area, the contact area of the material and an electrolyte is effectively improved, the sodium ion diffusion rate of the material is improved, and the three-dimensional network conductive carbon layer on the surface is beneficial to improving the electron conduction, thereby improving the reaction kinetics from the aspects of ion diffusion and electron transfer. Compared with the embodiment, the potassium vanadate nanobelt synthesized by the comparative example has the diameter of 200-300nm, and is not favorable for realizing rapid deintercalation of sodium ions, thereby affecting the diffusion rate of the sodium ions.
The positive electrode materials prepared in examples 1-2 and comparative examples 1-3 were subjected to XRD characterization, and the results are shown in FIG. 2. As can be seen from fig. 2Pure phase KV was synthesized in example 1, example 2, comparative example 1, comparative example 2 and comparative example 3 3 O 8 Corresponding to standard cards 00-022-1247.
The positive electrode materials obtained in examples 1-2 and comparative examples 1-3 above were subjected to a rate performance test in a sodium ion battery under the following conditions: a constant temperature oven for drying at room temperature of 25 ℃; the test results are shown in FIG. 3. As can be seen from fig. 3, the rate performance of example 1 and example 2 is significantly better than that of comparative examples 1 to 3. Comparative examples 1-3 exhibited 75.9mAh g, respectively, at 0.2C magnification -1 、78mAh g -1 、70.8mAh g -1 And examples 1 and 2 respectively showed 105mAh g -1 And 99.7mAh g -1 Is 27mAh g higher than comparative example 2 -1 And 21.7mAh g -1 . Wherein, by V 2 O 3 And V 2 O 5 Precursor method for preparing KV 3 O 8 Examples 1 and 2 of @ CNTs had specific capacities of 84.1mAh g, respectively, at a high magnification of 20C -1 And 89.3mAh g -1 Exhibits excellent rate performance. In comparative examples 1, 2 and 3, the specific capacities were 17.1mAh g at a high rate of 20C -1 ，34.4mAh g -1 And 33.5mAh g -1 Much lower than the rate capability of the examples.
The cathode materials obtained in examples 1-2 and comparative examples 1-3 were subjected to a cycle stability test in a sodium ion battery under the following conditions: a constant temperature oven for drying at room temperature of 25 ℃; the test results are shown in fig. 4. As can be seen from fig. 4, the cycle stability of example 1 and example 2 was also significantly better than that of comparative examples 1 to 3. Cycling 200 times at 1C magnification, examples 1 and 2 retained 82.5mAh g, respectively -1 And 80.7mAh g -1 While comparative examples 1 to 3 retained only 39.4mAh g after 200 cycles at a rate of 1C -1 ，45.1mAh g -1 And 44mAh g -1 And the specific discharge capacity of (c) indicates that the cycle stability is significantly lower than that of the examples.
The positive electrode materials obtained in examples 1-2 and comparative examples 1-3 were subjected to impedance tests in sodium ion batteries under the following conditions: a dry test platform at room temperature of 25 ℃; the test results are shown in fig. 5. As can be seen from fig. 5, the impedance of example 1 and example 2 is significantly smaller than that of comparative examples 1, 2 and 3, while the impedance of comparative example 1 is significantly larger than that of example 1, example 2, comparative example 2 and comparative example 3, which means that the surface conductivity of potassium vanadate composited by carbon nanotubes is significantly improved, and the three-dimensional network structure formed by cross-linking one-dimensional carbon nanotubes obtained in example 1-2 with potassium vanadate nanobelts is significantly better than that of amorphous carbon coated potassium vanadate of comparative example 2 and comparative example 3.
The positive electrode materials prepared in example 1 and comparative example 1 were subjected to nitrogen adsorption/desorption experiments, and the results are shown in fig. 6. As can be seen from FIG. 6, the specific surface area and pore size distribution of example 1 and comparative example 1 were measured by performing a nitrogen adsorption/desorption isothermal experiment, and the specific surface area of example 1 was 86m 2 g -1 Significantly higher than the 42m of the comparative example 2 g -1 The specific surface area and the embodiment have higher porosity, so that the contact area of the electrolyte and the electrode is larger in the charge and discharge process of the battery, more adsorption sites are provided for sodium ions, the reaction activity of the battery is greatly improved, the material reaction is more sufficient, and the effective capacity of the material can be greatly improved.
The circulation of the embodiment 1-2 under the low multiplying power shows higher specific capacity and good stability, and also shows good multiplying power performance under the high multiplying power, thereby being beneficial to improving the energy density of the sodium ion battery and having great significance in the research of the practicability of the positive electrode material of the sodium ion battery.
In addition, the potassium vanadate composite carbon nanotube electrode material prepared in example 1 was assembled as a positive electrode material of an aqueous zinc ion battery to form a button cell, and the button cell was subjected to electrochemical tests at room temperature under dry conditions, as shown in fig. 7 and 8, at 0.2. 0.2A g -1 Also exhibits 444.6mAh g at a current density of (C) -1 High specific discharge capacity of 20A g -1 Still retain 190mAh g at current density of (C) -1 Has good potential for large-scale energy storage.
Claims (8)
1. Metal ion battery positive electrode materialCharacterized in that the composition of the positive electrode material is KV 3 O 8 @CNTs; the positive electrode material is of a three-dimensional network structure formed by crosslinking a one-dimensional carbon nano tube and a potassium vanadate nano belt; the band diameter range of the positive electrode material is 10-150nm;
the preparation method of the metal ion battery anode material comprises the following steps:
1) Weighing a proper amount of vanadium source, drying and ball milling;
2) Adding a ball-milled vanadium source, a carbon nano tube, a reducing agent and a potassium source into a solvent to form a mixed solution, wherein the mass concentration of the solid content/solvent is 150-350mg/mL; the molar ratio of vanadium to reducing agent is 1 (0.9-1.1); the molar ratio of vanadium to potassium is 1 (3-5), and the mass fraction of the carbon nano tube to the vanadium source is 5-20%;
3) Stirring the mixed solution obtained in the step 2) in a water bath at the temperature of 30-50 ℃ for reaction for 5-8h; then, carrying out ultrasonic dispersion for 6-12 hours to obtain a mixture precursor, and transferring the mixture precursor into a reaction kettle;
4) Placing the reaction kettle in an oven at 120-180 ℃ for reaction for 12-48h;
5) Centrifuging the mixture after the reaction in the step 4) to obtain a precipitated product, washing and drying the precipitated product, and grinding to obtain the metal ion battery anode material.
2. The metal ion battery positive electrode material according to claim 1, wherein the positive electrode material has a band diameter in the range of 50-100nm.
3. The metal-ion battery positive electrode material of claim 1, wherein:
in the step 1), the steps of drying and ball milling are as follows: drying the vanadium source in an oven at 60-120 ℃ for 6-12h, transferring the dried vanadium source to a ball milling tank, and ball milling for 4-8h at 300-600r/min to obtain a ball milled vanadium source;
in the step 2), the mass concentration of the solid content/solvent in the mixed solution is 200-300mg/mL; the molar ratio of the vanadium to the reducing agent is 1:1; the molar ratio of the vanadium source to the potassium source is 1:4, the carbon nano tube accounts for 5-10% of the vanadium source by mass;
in the step 3), the water bath temperature is 30-40 ℃, the stirring time is 6-7 hours, and the ultrasonic dispersion time is 8-10 hours;
in the step 4), the reaction temperature is 120-150 ℃ and the reaction time is 24-36h;
in the step 5), the precipitated product is washed and dried in the following manner: washing with deionized water and ethanol for 2-5 times, and drying at 80-160deg.C for 8-18 hr.
4. A metal-ion battery positive electrode material according to claim 3, wherein:
in the step 1), the drying temperature is 80-100 ℃ and the drying time is 8-10h; ball milling speed is 400-500r/min, and ball milling time is 6-7h;
in the step 5), the precipitated product is washed and dried in the following manner: washing with deionized water for 3-4 times, and then washing with ethanol for 2-3 times; drying at 80-120deg.C for 8-16 hr.
5. The metal-ion battery positive electrode material of claim 1, wherein: the vanadium source is one or more than two of vanadium phosphate, ammonium metavanadate, vanadium pentoxide and vanadium trioxide, the carbon nanotubes are one or more than two of single-wall carbon nanotubes, multi-wall carbon nanotubes or few-wall carbon nanotubes, and the reducing agent is one or more than two of citric acid, oxalic acid, ascorbic acid, polyethylene glycol and hydrogen peroxide; the potassium source is one or more than two of potassium hydroxide, potassium oxalate, potassium sulfate, potassium citrate, potassium nitrate, potassium fluoride, potassium bicarbonate and potassium carbonate; the solvent is one or more of deionized water, ultrapure water and distilled water.
6. A metal ion battery positive electrode, characterized in that the metal ion battery positive electrode comprises the metal ion battery positive electrode material according to any one of claims 1 to 2.
7. A metal-ion battery comprising the metal-ion battery anode of claim 6.
8. The metal-ion battery of claim 7, wherein the metal-ion battery is a sodium-ion battery or an aqueous zinc-ion battery.
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| CN106898752A (en) * | 2017-03-31 | 2017-06-27 | 中南大学 | A kind of porous spherical vanadium phosphate sodium/carbon pipe composite positive pole and preparation method thereof |
| CN112952047A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery |
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| CN106898752A (en) * | 2017-03-31 | 2017-06-27 | 中南大学 | A kind of porous spherical vanadium phosphate sodium/carbon pipe composite positive pole and preparation method thereof |
| CN112952047A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery |
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