CN114242995B - Sodium ion battery nano sheet negative electrode material and preparation method and application thereof - Google Patents
Sodium ion battery nano sheet negative electrode material and preparation method and application thereof Download PDFInfo
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- CN114242995B CN114242995B CN202111340110.9A CN202111340110A CN114242995B CN 114242995 B CN114242995 B CN 114242995B CN 202111340110 A CN202111340110 A CN 202111340110A CN 114242995 B CN114242995 B CN 114242995B
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 73
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 73
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 10
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims 1
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- 238000005245 sintering Methods 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010405 anode material Substances 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000002064 nanoplatelet Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 6
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- 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 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a sodium ion battery nano sheet negative electrode material, a preparation method and application thereof. The preparation method of the sodium ion battery nano sheet negative electrode material comprises the following steps: firstly, carrying out solid-phase sintering, ion exchange and liquid-phase stripping on potassium salt, titanium oxide and niobium oxide to obtain electronegative TiNbO 5 nano-sheet dispersion liquid; then forming a TiNbO 5/graphene nano sheet heterostructure by electrostatic self-assembly with the electropositive graphene suspension, and freeze-drying the heterostructure to obtain the negative electrode material of the sodium ion battery nano sheet. The negative electrode material of the sodium ion battery nano sheet has a heterojunction built-in electric field, can promote rapid migration of sodium ions and electrons in the charge and discharge process of the battery, and shows excellent multiplying power performance and cycle stability.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery nano sheet negative electrode material, a preparation method and application thereof.
Background
The sodium ion battery has the advantages of low price, high safety and the like compared with the lithium ion battery because of abundant and widely distributed sodium resource reserves, and is expected to be applied to energy storage equipment in a large scale. However, compared with lithium ions, the radius of sodium ions is larger, and the volume change amplitude of the electrode material is larger in the charging and discharging process, so that the structure of the electrode material is damaged, and the rate performance and the cycle stability of the sodium ion battery are deteriorated.
For example, in the prior art, ultrathin layered niobium sulfide is used as a negative electrode material in a lithium/sodium ion battery, and the prepared niobium sulfide has a layered structure similar to graphene, and although the dynamic process of lithium/sodium ion intercalation/deintercalation is improved, the assembled sodium ion battery has poor rate capability and cycle stability and can only stably circulate for 100 circles under a small current density (0.5A/g).
Disclosure of Invention
The invention aims to overcome the defect and defect of poor rate capability and cycle stability of a sodium ion battery caused by the existing sodium ion negative electrode material, and provides a preparation method of a sodium ion battery nano sheet negative electrode material, wherein electronegative TiNbO 5 and electropositive graphene nano sheets are used as structural units, a regular and ordered superlattice heterojunction structure is formed by self-assembly under the action of electrostatic adsorption, and meanwhile, a built-in electric field of the heterojunction is constructed, so that rapid migration of sodium ions and electrons in the charge and discharge process is promoted, and further the rate capability and cycle stability of the sodium ion battery are improved.
The invention further aims to provide a negative electrode material of the sodium ion battery nano sheet.
The invention further aims to provide an application of the nano sheet negative electrode material of the sodium ion battery in the sodium ion battery.
The above object of the present invention is achieved by the following technical scheme:
the preparation method of the sodium ion battery nano sheet negative electrode material comprises the following steps:
S1, uniformly mixing potassium salt, titanium oxide and niobium oxide, calcining in inert atmosphere to obtain lamellar KTiNbO 5, acidizing, and performing ion exchange to obtain lamellar HTiNbO 5;
S2, uniformly mixing the layered HTiNbO 5 in S1 with tetrabutylammonium hydroxide and/or tetramethylammonium hydroxide aqueous solution, and stripping a liquid phase to obtain electronegative TiNbO 5 nano-sheet dispersion;
S3, adding the electropositive graphene suspension into the TiNbO 5 nano sheet dispersion liquid with electronegativity in the S2, self-assembling to form a TiNbO 5/graphene nano sheet heterojunction structure, and then freeze-drying to obtain a sodium ion battery nano sheet negative electrode material;
Wherein the potassium salt in S1: titanium oxide: the mole ratio of niobium oxide is 1:2: (0.5-3), wherein the temperature of the calcination treatment is 900-1200 ℃ and the calcination time is 15-30 h.
The invention needs to be described as follows:
Compared with the existing transition metal oxide nano-sheet negative electrode material, the nano-sheet negative electrode material of the sodium ion battery prepared by the invention has a plurality of valence states of Ti and Nb in TiNbO 5, and is favorable for multi-step sodium intercalation and deintercalation reaction, thereby improving the reversible specific capacity of the nano-sheet negative electrode material. Meanwhile, tiNbO 5 and the graphene nano-sheets can obviously shorten the diffusion distance of sodium ions and promote the migration of the sodium ions in the electrode material, so that the conductivity and the charge transfer dynamics of the transition metal oxide are improved. In addition, electronegative TiNbO 5 and electropositive graphene can form regularly and orderly stacked nano sheets through electrostatic self-assembly, so that agglomeration of the nano sheets is avoided, and a higher activity specific surface area and more sodium ion storage sites are maintained; the TiNbO 5 is wrapped between two layers of graphene, so that volume expansion and contraction of the TiNbO 5 nano sheet in the sodium removing and embedding process can be inhibited through a finite field effect; the electronegative TiNbO 5 and the electropositive graphene can also construct a built-in electric field to promote rapid migration of sodium ions and electrons, so that the rate performance and the cycling stability of the sodium ion battery are obviously improved.
The addition amount of niobium oxide affects the purity of the final TiNbO 5, and excessive or insufficient addition amount can produce more impurities. The calcination temperature is too low or the calcination time is too short, the reaction of the reactants is insufficient, and the purity of the calcined product is low; the calcining temperature is too high, so that the target product can undergo phase transformation to generate other substances.
Preferably, the potassium salt in S1: titanium oxide: the mole ratio of niobium oxide is 1:2: (1-3).
Preferably, the calcination treatment in S1 is carried out at a temperature of 1000-1100 ℃ for 20-30 hours.
Preferably, the electropositive graphene in S3: the mass ratio of the electronegative TiNbO 5 nano-sheet is 1:4 or 1:2.
Preferably, the potassium salt in S1: titanium oxide: the mole ratio of niobium oxide is 1:2:1, calcining treatment temperature is 1100 ℃, calcining time is 20h, and S3 is electropositive graphene: the mass ratio of the electronegative TiNbO 5 nano-sheet is 1:4.
Preferably, S2 is a dispersion of TiNbO 5 nano-sheets with electronegativity obtained by uniformly mixing layered HTiNbO 5 in S1 with tetrabutylammonium hydroxide aqueous solution and stripping the liquid phase.
The invention also protects the sodium ion battery nano sheet negative electrode material prepared by the preparation method.
The application of the sodium ion battery nano sheet negative electrode material in the sodium ion battery is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides a preparation method of a negative electrode material of a nano sheet of a sodium ion battery, which comprises the steps of preparing an electronegative TiNbO 5 nano sheet by adopting solid phase sintering and liquid phase stripping, and then self-assembling the electronegative TiNbO 5 nano sheet and the electropositive graphene nano sheet through electrostatic adsorption to form a regular and ordered superlattice heterojunction structure; meanwhile, an electric field built in the heterojunction is constructed by utilizing the electronegative TiNbO 5 and the electropositive graphene, so that rapid migration of sodium ions and electrons in the charge and discharge process is promoted, the assembled sodium ion battery has excellent rate performance and cycle stability, the first discharge specific capacity under 1A g -1 current is 114mAh g -1, and the capacity retention rate after 3000 circles is 98.8%.
Drawings
Fig. 1 is an X-ray diffraction pattern of the negative electrode material of the nanoplatelets in example 1.
Fig. 2 is SEM and TEM images of the negative electrode material of the nanoplatelets in example 1.
Fig. 3 is a view of a TiNbO 5/graphene nanoplatelet heterojunction scanning kelvin probe microscope.
Fig. 4 is a charge-discharge graph of a sodium ion battery assembled with the nanoplatelet anode material of example 1.
Fig. 5 is a cycle graph of a sodium ion battery assembled with the nanoplatelet anode material of example 1.
Fig. 6 is a cycle graph of a sodium ion battery assembled with the nanoplatelet anode material of comparative example 2.
Fig. 7 is a graph of the rate performance of sodium ion batteries assembled with the nanoplatelet anode materials of example 1, comparative example 1, and comparative example 2.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Example 1
The preparation method of the sodium ion battery nano sheet negative electrode material comprises the following steps:
S1, precursor K 2CO3、TiO2 and Nb 2O5 are mixed according to the molar ratio of 1:2:1, uniformly mixing, transferring the mixture into a platinum crucible, and placing the platinum crucible into a muffle furnace nitrogen atmosphere for calcining at 1100 ℃ for 20 hours to obtain a layered block KTiNbO 5; stirring and mixing 5g KTiNbO 5 and 1L of 1mol/L HCl for acid treatment for 7 days, replacing the HCl once a day, and obtaining a protonated HTiNbO 5 lamellar block through ion exchange;
S2, taking 0.4g of HTiNbO 5 powder in S1 according to the following ratio of n (TBA +)：n(H+) =1: 1, measuring a corresponding amount of 10% TBAOH aqueous solution, adding deionized water to 100mL, placing on a shaking table, and stripping for 7 days at a speed of 150rpm to obtain an electronegative single-layer TiNbO 5 nano-plate dispersion;
S3, dropwise adding the electropositive graphene suspension into the electronegative TiNbO 5 nano-sheet dispersion liquid in the S2, self-assembling the electropositive graphene and the electronegative TiNbO 5 through electrostatic adsorption to obtain a nano-sheet heterostructure with the TiNbO 5/graphene regularly and orderly arranged, and then performing centrifugal separation, deionized water rinsing and freeze drying treatment to obtain the sodium ion battery nano-sheet cathode material (TiNbO 5/rGO superlattice).
Wherein, the electropositive graphene suspension is prepared by the following preparation method:
A modified Hummers method was used to prepare graphene oxide suspension, 200mL of 0.2g/L graphene oxide suspension was measured again, 1.5mL of 20wt.% PDDA/H 2 O and 15. Mu.L hydrazine hydrate were added, stirred at 90℃for 3H, then centrifuged at 20000rpm, washed twice with deionized water, dispersed again in water, and centrifuged at 5000rpm to obtain an upper-layer electropositive graphene suspension.
Examples 2 to 11
The preparation methods of examples 2 to 11 are basically the same as those of example 1, and main experimental parameters are shown in table 1: a is the molar ratio of K 2CO3：TiO2：Nb2O5; b is the calcination temperature; c is the calcination time; d is electropositive graphene: the mass ratio of the electronegative TiNbO 5.
TABLE 1 Main Experimental parameters
| Numbering device | A | B | C | D |
| Example 2 | 1：2：0.5 | 1100℃ | 20h | 1：4 |
| Example 3 | 1：2：2 | 1100℃ | 20h | 1：4 |
| Example 4 | 1：2：3 | 1100℃ | 20h | 1：4 |
| Example 5 | 1：2：1 | 900℃ | 20h | 1：4 |
| Example 6 | 1：2：1 | 1000℃ | 20h | 1：4 |
| Example 7 | 1：2：1 | 1200℃ | 20h | 1：4 |
| Example 8 | 1：2：1 | 1100℃ | 15h | 1：4 |
| Example 9 | 1：2：1 | 1100℃ | 25h | 1：4 |
| Example 10 | 1：2：1 | 1100℃ | 30h | 1：4 |
| Example 11 | 1：2：1 | 1100℃ | 20h | 1：2 |
Comparative example 1
The preparation method of the sodium ion battery nano sheet negative electrode material comprises the following steps:
S1, precursor K 2CO3、TiO2 and Nb 2O5 are mixed according to the molar ratio of 1:2:1, uniformly mixing, transferring the mixture into a platinum crucible, and placing the platinum crucible into a muffle furnace for calcining at 1100 ℃ for 20 hours in the nitrogen atmosphere to obtain a layered block KTiNbO 5; stirring and mixing 5g KTiNbO 5 and 1L of 1mol/L HCl for acid treatment for 7 days, replacing the HCl once a day, and obtaining a protonated HTiNbO 5 lamellar block through ion exchange;
S2. 0.4g htisbo 5 powder was mixed according to n (TBA +)：n(H+) =1: 1, measuring a corresponding amount of 10% TBAOH aqueous solution, adding deionized water to 100mL, placing on a shaking table, and stripping for 7 days at a speed of 150rpm to obtain an electronegative single-layer TiNbO 5 nano-sheet dispersion, and freeze-drying to obtain the sodium ion battery nano-sheet negative electrode material (TiNbO 5).
Comparative example 2
The preparation method of the sodium ion battery nano sheet negative electrode material comprises the following steps:
S1, precursor K 2CO3、TiO2 and Nb 2O5 are mixed according to the molar ratio of 1:2:1, uniformly mixing, transferring the mixture into a platinum crucible, and placing the platinum crucible into a muffle furnace for calcining at 1100 ℃ for 20 hours in the nitrogen atmosphere to obtain a layered block KTiNbO 5; stirring and mixing 5g KTiNbO 5 and 1L of 1mol/L HCl for acid treatment for 7 days, replacing the HCl once a day, and obtaining a protonated HTiNbO 5 lamellar block through ion exchange;
S2, taking 0.4g of HTiNbO 5 powder in S1 according to the following ratio of n (TBA +)：n(H+) =1: 1, measuring a corresponding amount of 10% TBAOH aqueous solution, adding deionized water to 100mL, placing on a shaking table, and stripping for 7 days at a speed of 150rpm to obtain an electronegative single-layer TiNbO 5 nano-sheet dispersion, and freeze-drying to obtain TiNbO 5 nano-sheet powder;
S3, freeze-drying the graphene suspension, mixing with the TiNbO 5 nano-sheet powder in the S2, and uniformly grinding to obtain the sodium ion battery nano-sheet negative electrode material (TiNbO 5/rGO is simply mixed).
Result detection
(1) X-ray diffraction test
The X-ray diffraction pattern of the negative electrode material of the sodium ion nano-sheet in the example 1 is shown in fig. 1, and a diffraction peak appears at 6.6 degrees, and the d value of the diffraction peak is 1.3nm; the sum of the crystallographic thicknesses of TiNbO 5 and graphene is 2.6nm and is just twice the d value of the diffraction peak, which indicates that TiNbO 5 and graphene nanolayers are regularly and orderly arranged, and the 6.6-degree position is the (002) second-order diffraction peak of the TiNbO 5/graphene superlattice heterojunction.
(2) SEM and TEM testing
In the embodiment 1, the SEM image of the nano-sheet negative electrode material of the sodium ion battery is shown in fig. 2 (left image), the TEM image is shown in fig. 2 (right image), and the test result shows that the nano-sheet negative electrode material presents a loose porous structure, so that the agglomeration of the nano-sheet is effectively reduced, and the dispersibility of the sodium ion nano-sheet negative electrode material is remarkably improved.
(3) Scanning electron microscope test for Kelvin probe
The specific test method comprises the following steps: firstly, sequentially depositing a single-layer TiNbO 5 nano sheet and a single-layer graphene nano sheet on a silicon wafer substrate, and then observing the surface potential of the single-layer TiNbO 5 nano sheet and the single-layer graphene nano sheet by using a scanning Kelvin probe scanning electron microscope.
The test results are shown in fig. 3, and it can be seen from the graph that the potential difference between the two nano-sheets is about 50mV, which indicates that the electronegative TiNbO 5 and the electropositive graphene can form a built-in electric field.
(4) Battery performance test
The specific test method comprises the following steps: the negative electrode materials of the sodium ion battery nano-sheets prepared in the examples and the comparative examples are used as active substances, acetylene black is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, and the mass ratio is 7:2:1, adding a proper amount of N-methyl-2-pyrrolidone (NMP), uniformly stirring, coating on a copper foil, vacuum drying at 90 ℃ to constant weight, and finally blanking into an electrode slice with the diameter of 10mm for standby.
1Mol/L NaClO 4/EC+DMC (V: V=1:1) is used as electrolyte, and glass fiber (GF/D) is used as a diaphragm; and (3) taking the electrode plate as a working electrode, taking the metal sodium plate as a counter electrode, and assembling the CR2032 button cell in an argon atmosphere glove box.
The cycling performance and the multiplying power performance of the CR2032 button cell are tested by adopting a blue charge-discharge tester, the charge-discharge test voltage window is 0.01-3V, the current density of the cycling performance test is 1.0Ag -1, the cycling performance result of the sodium ion cell assembled by the cathode material in the embodiment 1 is shown as figure 5, the initial discharge specific capacity is 114mAh g -1, the capacity retention rate is 98.8% after 3000 circles of stable circulation, and the excellent cycling stability is shown; the cycle performance result of the sodium-ion battery assembled by the anode material in comparative example 2 is shown in fig. 6, the specific capacity of the first discharge is 98mAh g -1, the capacity retention rate after 3000 stable cycles is 91%, which indicates that compared with the anode material (comparative example 2) obtained by simply mixing TiNbO 5/rGO, the TiNbO 5/rGO superlattice anode material (example 1) has more excellent cycle stability.
The charge-discharge curve of the sodium ion battery assembled by the sodium ion nano-sheet negative electrode material in example 1 is shown in fig. 4, and it can be seen from the graph that TiNbO 5/graphene shows a higher first-circle specific capacity 1099mAh g -1, a second-circle specific capacity 409mAh g -1, and a coulomb efficiency of 90%.
The current densities of the rate performance tests are 0.05Ag -1、0.1A g-1、0.2A g-1、0.5A g-1、1.0A g-1、2.0A g-1 and 5.0A g -1 respectively, and the test results are shown in table 2 and fig. 7, and it can be seen from the graph that the specific capacities of the sodium ion battery assembled by the anode material in example 1 under different current densities are higher than the specific capacities corresponding to the same current densities in comparative example 1 and comparative example 2, which indicates that compared with the anode material (comparative example 2) obtained by simply mixing the TiNbO 5 anode material (comparative example 1) and the TiNbO 5/rGO, the TiNbO 5/rGO superlattice anode material (example 1) formed by self-assembly through electrostatic adsorption can utilize the electronegative TiNbO 5 and the electropositive graphene to construct a built-in electric field, promote rapid migration of sodium ions and electrons in the charge-discharge process, and have more excellent rate performance.
TABLE 2 rate capability
| Current density | Example 1 | Comparative example 1 | Comparative example 2 |
| 0.05A g-1 | 247mAh g-1 | 91mAh g-1 | 205mAh g-1 |
| 0.1A g-1 | 216mAh g-1 | 75mAh g-1 | 177mAh g-1 |
| 0.2A g-1 | 183mAh g-1 | 59mAh g-1 | 152mAh g-1 |
| 0.5A g-1 | 144mAh g-1 | 30mAh g-1 | 120mAh g-1 |
| 1.0A g-1 | 115mAh g-1 | 10mAh g-1 | 98mAh g-1 |
| 2.0A g-1 | 83mAh g-1 | 3mAh g-1 | 73mAh g-1 |
| 5.0A g-1 | 45mAh g-1 | 0.5mAh g-1 | 40mAh g-1 |
TABLE 3 cycle performance
As can be seen from Table 3, the sodium ion batteries assembled by the negative electrode materials in examples 1 to 11 of the invention have a specific capacity of 103 to 114mAh g -1 after initial discharge at a current density of 1A g -1, and a capacity retention rate of 95.6 to 98.8% after 3000 cycles; the sodium ion batteries assembled by the anode materials in comparative examples 1 and 2 have initial discharge specific capacities of 18mAh g -1 and 98mAh g -1 at a current density of 1A g -1, and capacity retention rates after 3000 cycles of 83.3% and 91% respectively, so that the anode materials (examples 1 to 11) formed by self-assembly through electrostatic adsorption have better cycle stability than the anode materials (comparative example 2) obtained by simply mixing the TiNbO 5 anode material (comparative example 1) and the TiNbO 5/rGO.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The preparation method of the sodium ion battery nano sheet negative electrode material is characterized by comprising the following steps of:
S1, uniformly mixing potassium salt, titanium oxide and niobium oxide, calcining in inert atmosphere to obtain lamellar KTiNbO 5, acidizing, and performing ion exchange to obtain lamellar HTiNbO 5;
S2, uniformly mixing the layered HTiNbO 5 in S1 with tetrabutylammonium hydroxide and/or tetramethylammonium hydroxide aqueous solution, and stripping a liquid phase to obtain electronegative TiNbO 5 nano-sheet dispersion;
S3, adding the electropositive graphene suspension into the TiNbO 5 nano sheet dispersion liquid with electronegativity in the S2, self-assembling to form a TiNbO 5/graphene nano sheet heterojunction structure, and then freeze-drying to obtain a sodium ion battery nano sheet negative electrode material;
Wherein the potassium salt in S1: titanium oxide: the mole ratio of niobium oxide is 1:2: (0.5-3), wherein the temperature of the calcination treatment is 900-1200 ℃ and the calcination time is 15-30 h;
The electropositive graphene suspension in S3 is prepared by the following preparation method:
A modified Hummers method was used to prepare graphene oxide suspension, 200mL of 0.2g/L graphene oxide suspension was measured again, 1.5mL of 20wt.% PDDA/H 2 O and 15. Mu.L hydrazine hydrate were added, stirred at 90℃for 3H, then centrifuged at 20000rpm, washed twice with deionized water, dispersed again in water, and centrifuged at 5000rpm to obtain an upper-layer electropositive graphene suspension.
2. The method for preparing a negative electrode material of a nano sheet of a sodium ion battery according to claim 1, wherein the potassium salt in S1: titanium oxide: the mole ratio of niobium oxide is 1:2: (1-3).
3. The method for preparing the negative electrode material of the sodium ion battery nano sheet according to claim 2, wherein the calcining treatment temperature in the S1 is 1000-1100 ℃ and the calcining time is 20-30 h.
4. The method for preparing a negative electrode material of a nano sheet for a sodium ion battery according to claim 3, wherein the electropositive graphene in S3: the mass ratio of the electronegative TiNbO 5 nano-sheet is 1:4 or 1:2.
5. The method for preparing a negative electrode material of a sodium ion battery nano sheet according to claim 4, wherein the potassium salt in S1: titanium oxide: the mole ratio of niobium oxide is 1:2:1, the calcination treatment temperature is 1100 ℃, the calcination time is 20h, and the electropositive graphene in S3: the mass ratio of the electronegative TiNbO 5 nano-sheet is 1:4.
6. The method for preparing the negative electrode material of the nano sheet of the sodium ion battery according to claim 1, wherein S2 is a dispersion liquid of the nano sheet of the electronegative TiNbO 5 obtained by uniformly mixing and liquid-phase stripping the layered HTiNbO 5 in S1 and a tetrabutylammonium hydroxide aqueous solution.
7. A negative electrode material for sodium ion battery obtained by the method for preparing a negative electrode material for sodium ion battery according to any one of claims 1 to 6.
8. Use of the negative electrode material of the nano sheet of the sodium ion battery in the sodium ion battery.
9. A sodium ion battery, which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is prepared from raw materials comprising the sodium ion battery nano-sheet negative electrode material of claim 7.
10. The sodium ion battery of claim 9, wherein the separator is fiberglass.
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