CN114242995A - Sodium ion battery nanosheet negative electrode material and preparation method and application thereof - Google Patents
Sodium ion battery nanosheet negative electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114242995A CN114242995A CN202111340110.9A CN202111340110A CN114242995A CN 114242995 A CN114242995 A CN 114242995A CN 202111340110 A CN202111340110 A CN 202111340110A CN 114242995 A CN114242995 A CN 114242995A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- nanosheet
- negative electrode
- sodium
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002135 nanosheet Substances 0.000 title claims abstract description 81
- 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 65
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 9
- 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 9
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000010405 anode material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001338 self-assembly Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 239000010406 cathode material Substances 0.000 abstract description 6
- 230000005684 electric field Effects 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 4
- 238000000707 layer-by-layer assembly Methods 0.000 abstract description 2
- 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
- 238000012360 testing method Methods 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 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
- 239000002033 PVDF binder Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000523 sample Substances 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
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 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
- 239000010955 niobium Substances 0.000 description 2
- 238000011056 performance test Methods 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
- 229910001868 water Inorganic materials 0.000 description 2
- 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 description 1
- 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
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-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
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 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
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 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
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 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
- 229910001488 sodium perchlorate Inorganic materials 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
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
Abstract
The invention discloses a sodium ion battery nanosheet negative electrode material and a preparation method and application thereof. The preparation method of the sodium ion battery nanosheet negative electrode material comprises the following steps: firstly, potassium salt, titanium oxide and niobium oxide are subjected to solid-phase sintering, ion exchange and liquid-phase stripping to obtain electronegative TiNbO5A nanosheet dispersion; then forming TiNbO with electropositive graphene suspension through electrostatic self-assembly5And/or carrying out freeze drying on the graphene nanosheet heterostructure to obtain the sodium ion battery nanosheet cathode material. The nano-sheet negative electrode material for the sodium-ion battery has a heterojunction built-in electric field, can promote the rapid migration of sodium ions and electrons in the charging and discharging processes of the battery, and shows excellent rate capability and cycle stability.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery nanosheet negative electrode material and a preparation method and application thereof.
Background
The sodium ion battery has the advantages of low price, high safety and the like compared with a lithium ion battery due to rich sodium resource reserves and wide distribution, 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 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 capability and the cycle stability of the sodium ion battery are poor.
For example, in the prior art, ultra-thin layer niobium sulfide is used as a negative electrode material in a lithium/sodium ion battery, the prepared niobium sulfide has a graphene-like layered structure, and although the dynamic process of lithium/sodium ion intercalation/deintercalation is improved, the rate performance and the cycling stability of the assembled sodium ion battery are poor, and the battery can only stably cycle for 100 cycles at a low current density (0.5A/g).
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of poor rate performance and poor cycle stability of a sodium ion battery caused by the conventional sodium ion negative electrode material, and provides a preparation method of a sodium ion battery nanosheet negative electrode material, which is prepared from electronegative TiNbO5And the electropositive graphene nanosheets are structural units, a regular and ordered superlattice heterojunction structure is formed through self-assembly under the electrostatic adsorption effect, and a built-in electric field of the heterojunction is constructed, so that the rapid migration of sodium ions and electrons in the charging and discharging process is promoted, and the rate capability and the cycling stability of the sodium ion battery are further improved.
The invention also aims to provide a nanosheet anode material for a sodium-ion battery.
The invention further aims to provide an application of the nanosheet negative electrode material of the sodium-ion battery in the sodium-ion battery.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a sodium ion battery nanosheet negative electrode material comprises the following steps:
s1, mixing potassium salt, titanium oxide and niobium oxideMixing uniformly, and then calcining in inert atmosphere to obtain laminar KTiNbO5Then, the mixture is acidified to obtain layered HTiNbO by ion exchange5；
S2, mixing the layered HTiNbO in S15Uniformly mixing with tetrabutylammonium hydroxide and/or tetramethylammonium hydroxide aqueous solution, and stripping liquid phase to obtain electronegative TiNbO5A nanosheet dispersion;
s3, adding the electropositive graphene suspension into the electronegative TiNbO in S25Self-assembly of the nano-sheet dispersion to form TiNbO5A graphene nanosheet heterojunction structure is adopted, and then freeze drying is carried out to obtain a sodium ion battery nanosheet negative electrode material;
wherein the potassium salt in S1: titanium oxide: the molar ratio of niobium oxide is 1: 2: (0.5-3), wherein the calcining treatment temperature is 900-1200 ℃, and the calcining time is 15-30 h.
The invention needs to be explained as follows:
compared with the conventional transition metal oxide nanosheet cathode material, the prepared sodium ion battery nanosheet cathode material has the advantages of TiNbO5Ti and Nb in the alloy have multiple valence states, which is beneficial to carrying out multi-step sodium intercalation reaction, thereby improving the reversible specific capacity of the alloy. Meanwhile, TiNbO5And the graphene nanosheet 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 charge transfer kinetics of the transition metal oxide are improved. In addition, electronegative TiNbO5The graphene and the electropositive graphene can form regularly and orderly stacked nanosheets through electrostatic self-assembly, so that agglomeration of the nanosheets is avoided, and higher active specific surface area and more sodium ion storage sites are maintained; TiNbO5Is wrapped between two layers of graphene and can inhibit TiNbO through a confinement effect5The volume expansion and contraction of the nano-sheets caused in the process of sodium intercalation; electronegative TiNbO5And the graphene with the electropositive property can also construct a built-in electric field to promote the rapid migration of sodium ions and electrons, so that the rate capability and the cycling stability of the sodium ion battery are remarkably improved.
The addition amount of niobium oxide will beInfluence on Final TiNbO5Too much or too little of the purity of (2) causes generation of many impurities. The calcination temperature is too low or the calcination time is too short, each reactant has insufficient reaction, and the purity of the calcination product is low; if the calcination temperature is too high, the target product will undergo phase transition to generate other substances.
Preferably, the ratio of potassium salt in S1: titanium oxide: the molar ratio of niobium oxide is 1: 2: (1-3).
Preferably, the calcining treatment in S1 is carried out at 1000-1100 ℃ for 20-30 h.
Preferably, the electropositive graphene in S3: electronegative TiNbO5The mass ratio of the nano sheets is 1: 4 or 1: 2.
preferably, the ratio of potassium salt in S1: titanium oxide: the molar ratio of niobium oxide is 1: 2: 1, the temperature of the calcination treatment is 1100 ℃, the calcination time is 20h, and the electropositive graphene in S3: electronegative TiNbO5The mass ratio of the nano sheets is 1: 4.
preferably, S2 is layered HTiNbO in S15Uniformly mixing with tetrabutyl ammonium hydroxide aqueous solution, and stripping liquid phase to obtain electronegative TiNbO5A nanosheet dispersion.
The invention also provides a sodium ion battery nanosheet negative electrode material prepared by the preparation method.
The invention also discloses application of the nanosheet negative electrode material of the sodium-ion battery in the sodium-ion battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a sodium ion battery nanosheet negative electrode material, which is used for preparing electronegative TiNbO by adopting solid-phase sintering and liquid-phase stripping5The nano sheet and an electropositive graphene nano sheet are self-assembled through electrostatic adsorption to form a regular and ordered superlattice heterojunction structure; TiNbO using electronegativity simultaneously5An electropositive graphene is used for constructing a heterojunction built-in electric field, rapid migration of sodium ions and electrons in the charge and discharge process is promoted, the assembled sodium ion battery shows excellent rate capability and cycle stability, 1A g-1The first discharge specific capacity under current is 114mAh g-1And the capacity retention rate after 3000 cycles is 98.8%.
Drawings
Fig. 1 is an X-ray diffraction pattern of the nanosheet anode material of example 1.
Fig. 2 is SEM and TEM images of the nanosheet anode material of example 1.
FIG. 3 is TiNbO5And/scanning a Kelvin probe microscope atlas by the graphene nanosheet heterojunction.
Fig. 4 is a charge-discharge curve diagram of the sodium ion battery assembled by the nanosheet negative electrode material in example 1.
Fig. 5 is a cycle curve diagram of a sodium ion battery assembled by nanosheet anode materials in example 1.
Fig. 6 is a cycle plot of a sodium ion battery assembled with nanosheet anode material of comparative example 2.
Fig. 7 is a graph of rate performance of sodium ion batteries assembled with nanosheet anode materials in example 1, comparative example 1, and comparative example 2.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A preparation method of a sodium ion battery nanosheet negative electrode material comprises the following steps:
s1, mixing a precursor K2CO3、TiO2And Nb2O5The molar ratio of the raw materials is 1: 2: 1, then transferring the mixture into a platinum crucible, and calcining the mixture for 20 hours at 1100 ℃ in a muffle furnace nitrogen atmosphere to obtain layered bulk KTiNbO5(ii) a 5g of KTiNbO5Stirring and mixing with 1L of 1mol/L HCl, performing acid treatment for 7 days, replacing HCl once a day, and obtaining protonated HTiNbO by ion exchange5A layered block;
s2, taking HTiNbO in 0.4g S15Powder of n (TBA)+)：n(H+)＝1: 1, measuring a corresponding amount of 10% TBAOH aqueous solution, adding deionized water to 100mL, placing on a shaker, stripping at the speed of 150rpm for 7 days to obtain electronegative single-layer TiNbO5A nanosheet dispersion;
s3, dropwise adding the electropositive graphene suspension into the electronegative TiNbO in S25The nano-sheet dispersion liquid is prepared by using electropositive graphene and electronegative TiNbO through electrostatic adsorption5Self-assembling to obtain TiNbO5Carrying out centrifugal separation, deionized water rinsing and freeze drying treatment on the nano sheet heterostructure in which graphene is regularly and orderly arranged to obtain the nano sheet cathode material (TiNbO) of the sodium ion battery5a/rGO superlattice).
The electropositive graphene suspension is prepared by the following preparation method:
preparing graphene oxide suspension by adopting an improved Hummers method, measuring 200mL of 0.2g/L graphene oxide suspension, and adding 1.5mL of 20 wt.% PDDA/H2O and 15 mu L of hydrazine hydrate, stirring for 3h at 90 ℃, then centrifuging at 20000rpm, washing twice with deionized water, dispersing in water again, and centrifuging at 5000rpm to obtain the upper electropositive graphene suspension.
Examples 2 to 11
The preparation method of the embodiments 2-11 is basically the same as that of the embodiment 1, and the main experimental parameters are shown in the table 1: a is K2CO3：TiO2：Nb2O5The molar ratio of (A) to (B); b is the calcination temperature; c is calcination time; d is electropositive graphene: electronegative TiNbO5The mass ratio of (a).
TABLE 1 Main Experimental parameters
| Numbering | 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
A preparation method of a sodium ion battery nanosheet negative electrode material comprises the following steps:
s1, mixing a precursor K2CO3、TiO2And Nb2O5The molar ratio of the raw materials is 1: 2: 1, uniformly mixing, transferring the mixture into a platinum crucible,calcining at 1100 ℃ for 20 hours in a muffle furnace in nitrogen atmosphere to obtain layered bulk KTiNbO5(ii) a 5g of KTiNbO5Stirring and mixing with 1L of 1mol/L HCl, performing acid treatment for 7 days, replacing HCl once a day, and obtaining protonated HTiNbO by ion exchange5A layered block;
s2, adding 0.4g of HTiNbO5Powder of n (TBA)+)：n(H+) 1: 1, measuring a corresponding amount of 10% TBAOH aqueous solution, adding deionized water to 100mL, placing on a shaker, and stripping at the speed of 150rpm for 7 days to obtain electronegative single-layer TiNbO5The nano-sheet dispersion liquid is frozen and dried to obtain the nano-sheet cathode material (TiNbO) of the sodium ion battery5)。
Comparative example 2
A preparation method of a sodium ion battery nanosheet negative electrode material comprises the following steps:
s1, mixing a precursor K2CO3、TiO2And Nb2O5The molar ratio of the raw materials is 1: 2: 1, then transferring the mixture into a platinum crucible, and calcining the mixture for 20 hours at 1100 ℃ in a muffle furnace in nitrogen atmosphere to obtain layered bulk KTiNbO5(ii) a 5g of KTiNbO5Stirring and mixing with 1L of 1mol/L HCl, performing acid treatment for 7 days, replacing HCl once a day, and obtaining protonated HTiNbO by ion exchange5A layered block;
s2, taking HTiNbO in 0.4g S15Powder of n (TBA)+)：n(H+) 1: 1, measuring a corresponding amount of 10% TBAOH aqueous solution, adding deionized water to 100mL, placing on a shaker, and stripping at the speed of 150rpm for 7 days to obtain electronegative single-layer TiNbO5The nano-sheet dispersion liquid is frozen and dried to obtain TiNbO5Nanosheet powder;
s3, freeze-drying the graphene suspension and TiNbO in S25Mixing the nano-sheet powder, and uniformly grinding to obtain the nano-sheet cathode material (TiNbO) of the sodium-ion battery5Simple mix/rGO).
Result detection
(1) X-ray diffraction test
X of the negative electrode material of sodium ion nanosheet in example 1The ray diffraction pattern is shown in figure 1, a diffraction peak appears at 6.6 degrees, and the d value is 1.3 nm; and TiNbO5And the sum of the crystallographic thickness of the graphene is 2.6nm, which is just twice of the d value of the diffraction peak, and the result shows that TiNbO5And graphene nanolayers are regularly and orderly arranged, and the position of 6.6 degrees is TiNbO5(002) second order diffraction peak of graphene superlattice heterojunction.
(2) SEM and TEM testing
In example 1, an SEM image of the sodium ion battery nanosheet negative electrode material is shown in fig. 2 (left image), and a TEM image is shown in fig. 2 (right image), and test results show that the nanosheet negative electrode material has a loose porous structure, so that agglomeration of the nanosheets is effectively reduced, and dispersibility of the sodium ion nanosheet negative electrode material is significantly improved.
(3) Scanning Kelvin probe scanning electron microscope test
The specific test method comprises the following steps: firstly, sequentially depositing single-layer TiNbO on a silicon wafer substrate5And (3) using the nano sheets and the graphene nano sheets, and then observing the surface potential of the nano sheets and the graphene nano sheets by using a scanning Kelvin probe scanning electron microscope.
The test results are shown in FIG. 3, from which it can be seen that the potential difference between the two nanosheets is about 50mV, indicating an electronegative TiNbO5And electropositive graphene can form a built-in electric field.
(4) Battery performance testing
The specific test method comprises the following steps: taking the sodium-ion battery nanosheet negative electrode materials prepared in the examples and the comparative examples as active materials, acetylene black as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, and mixing the active materials and the polyvinylidene fluoride (PVDF) according to the mass ratio of 7: 2: 1, adding a proper amount of N-methyl-2-pyrrolidone (NMP), uniformly stirring, coating on a copper foil, drying in vacuum at 90 ℃ to constant weight, and finally blanking into electrode slices with the diameter of 10mm for later use.
At 1mol/L of NaClO4The electrolyte is/EC + DMC (V: V is 1: 1), and the diaphragm is glass fiber (GF/D); and assembling the CR2032 button cell in an argon atmosphere glove box by taking the electrode slice as a working electrode and a metal sodium slice as a counter electrode.
Adopt blue electricity to charge and discharge the tester to test the above-mentioned CR2032 type button cellThe cycle performance and the rate performance are realized, the voltage window of a charge and discharge test is 0.01-3V, and the current density of the cycle performance test is 1.0Ag-1The cycle performance results of the sodium ion battery assembled by the negative electrode material in example 1 are shown in fig. 5, and the specific first discharge capacity is 114mAh g-1The capacity retention rate is 98.8% after 3000 circles of stable circulation, and excellent circulation stability is shown; the cycle performance results of the sodium ion battery assembled by the negative electrode material in the comparative example 2 are shown in fig. 6, and the first discharge specific capacity is 98mAh g-1The capacity retention rate after 3000 cycles of stable cycling was 91%, indicating that compared to TiNbO5Negative electrode material (comparative example 2), TiNbO, simply mixed with/rGO5the/rGO superlattice negative electrode material (example 1) has more excellent cycling stability.
The charging and discharging curve of the sodium ion battery assembled by the sodium ion nanosheet negative electrode material in example 1 is shown in fig. 4, from which TiNbO can be seen5The graphene shows higher first-circle specific capacity of 1099mAh g-1The specific capacity of the second ring is 409mAh g-1The coulombic efficiency was 90%.
The current density of the multiplying power performance test is 0.05Ag respectively-1、0.1A g-1、0.2A g-1、0.5A g-1、1.0A g-1、2.0A g-1And 5.0A g-1The test results are shown in table 2 and fig. 7, and it can be seen from the figures that the specific capacity of the sodium ion battery assembled by the negative electrode material in example 1 under different current densities is higher than that of comparative example 1 and comparative example 2 under the same current density, which shows that compared with the pure TiNbO5Negative electrode Material (comparative example 1) and TiNbO5Negative electrode material (comparative example 2) obtained by simply mixing/rGO and TiNbO formed by self-assembly through electrostatic adsorption5the/rGO superlattice negative electrode material (example 1) can utilize electronegative TiNbO5And an electropositive graphene is used for constructing a heterojunction built-in electric field, so that the rapid migration of sodium ions and electrons in the charge and discharge process is promoted, and the graphene has more excellent rate capability.
TABLE 2 Rate Performance
| 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 cyclability
As can be seen from Table 3, the sodium ion batteries assembled by the negative electrode materials in examples 1-11 of the present invention are 1A g-1The first discharge specific capacity under the current density is 103-114 mAh g-1The capacity retention rate after 3000 circles of circulation is 95.6-98.8%; while the sodium ion batteries assembled by the negative electrode materials in comparative examples 1 and 2 are at 1A g-1The first discharge specific capacity under the current density is respectively 18mAh g-1And 98mAh g-1The capacity retention after 3000 cycles was 83.3% and 91%, respectively, thus demonstrating the comparison with pure TiNbO5Negative electrode Material (comparative example 1) and TiNbO5Negative electrode material (comparative example 2) obtained by simply mixing/rGO and TiNbO formed by self-assembly through electrostatic adsorption5the/rGO superlattice negative electrode materials (examples 1-11) have more excellent cycling stability.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a sodium ion battery nanosheet negative electrode material is characterized by comprising the following steps:
s1, mixing potassium salt, titanium oxide and niobium oxide uniformly, and then calcining in an inert atmosphere to obtain laminar KTiNbO5Then, the mixture is acidified to obtain layered HTiNbO by ion exchange5；
S2, mixing the layered HTiNbO in S15Uniformly mixing with tetrabutylammonium hydroxide and/or tetramethylammonium hydroxide aqueous solution, and stripping liquid phase to obtain electronegative TiNbO5A nanosheet dispersion;
s3, adding the electropositive graphene suspension into the electronegative TiNbO in S25Self-assembly of the nano-sheet dispersion to form TiNbO5A graphene nanosheet heterojunction structure is adopted, and then freeze drying is carried out to obtain a sodium ion battery nanosheet negative electrode material;
wherein the potassium salt in S1: titanium oxide: the molar ratio of niobium oxide is 1: 2: (0.5-3), wherein the calcining treatment temperature is 900-1200 ℃, and the calcining time is 15-30 h.
2. A method for preparing a nano-sheet anode material of a sodium-ion battery as claimed in claim 1, wherein the ratio of potassium salt in S1: titanium oxide: the molar ratio of niobium oxide is 1: 2: (1-3).
3. A preparation method of a sodium ion battery nanosheet negative electrode material as claimed in claim 2, wherein the calcining treatment in S1 is carried out at a temperature of 1000-1100 ℃ for a time of 20-30 h.
4. A method for preparing a sodium ion battery nanosheet negative electrode material as recited in claim 3, wherein the electropositive graphene in S3: electronegative TiNbO5The mass ratio of the nano sheets is 1: 4 or 1: 2.
5. a preparation method of a sodium-ion battery nanosheet anode material according to claim 4, wherein the potassium salt: titanium oxide: the molar ratio of niobium oxide is 1: 2: 1, the temperature of the calcination treatment is 1100 ℃, the calcination time is 20h, and the electropositive graphene in S3: electronegative TiNbO5The mass ratio of the nano sheets is 1: 4.
6. a preparation method of sodium-ion battery nanosheet negative electrode material as claimed in claim 1, wherein S2 is layered HTiNbO in S15Uniformly mixing with tetrabutyl ammonium hydroxide aqueous solution, and stripping liquid phase to obtain electronegative TiNbO5A nanosheet dispersion.
7. A sodium ion battery nanosheet negative electrode material obtained by the preparation method of the sodium ion battery nanosheet negative electrode material according to any one of claims 1 to 6.
8. Application of the sodium-ion battery nanosheet negative electrode material of claim 7 in a sodium-ion battery.
9. A sodium-ion battery is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is prepared from a raw material comprising the sodium-ion battery nanosheet negative electrode material of claim 7.
10. The sodium-ion battery of claim 9, wherein the separator is a glass fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111340110.9A CN114242995A (en) | 2021-11-12 | 2021-11-12 | Sodium ion battery nanosheet negative electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111340110.9A CN114242995A (en) | 2021-11-12 | 2021-11-12 | Sodium ion battery nanosheet negative electrode material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114242995A true CN114242995A (en) | 2022-03-25 |
Family
ID=80749221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111340110.9A Pending CN114242995A (en) | 2021-11-12 | 2021-11-12 | Sodium ion battery nanosheet negative electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114242995A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043441A (en) * | 2022-07-28 | 2022-09-13 | 温州大学碳中和技术创新研究院 | Preparation method of layered oxide positive electrode material based on three-phase heterogeneous symbiotic structure and sodium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013157335A (en) * | 2013-04-30 | 2013-08-15 | Toshiba Corp | Method for producing negative electrode active material for battery |
| KR20140049190A (en) * | 2012-10-16 | 2014-04-25 | 이화여자대학교 산학협력단 | Preparing method of nano-colloids of layered niobium-containing metal oxide, nano-colloids of layered niobium-containing metal oxide produced thereby and preparing method of highly dielectric thin film using the same |
| US20170225233A1 (en) * | 2016-02-09 | 2017-08-10 | Aruna Zhamu | Chemical-free production of graphene-reinforced inorganic matrix composites |
| EP3219675A1 (en) * | 2016-03-16 | 2017-09-20 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack, and vehicle |
| CN107369829A (en) * | 2017-06-30 | 2017-11-21 | 陕西科技大学 | A kind of preparation method of lithium ion battery Mao Danzhuan niobium oxide electrode materials |
-
2021
- 2021-11-12 CN CN202111340110.9A patent/CN114242995A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140049190A (en) * | 2012-10-16 | 2014-04-25 | 이화여자대학교 산학협력단 | Preparing method of nano-colloids of layered niobium-containing metal oxide, nano-colloids of layered niobium-containing metal oxide produced thereby and preparing method of highly dielectric thin film using the same |
| JP2013157335A (en) * | 2013-04-30 | 2013-08-15 | Toshiba Corp | Method for producing negative electrode active material for battery |
| US20170225233A1 (en) * | 2016-02-09 | 2017-08-10 | Aruna Zhamu | Chemical-free production of graphene-reinforced inorganic matrix composites |
| EP3219675A1 (en) * | 2016-03-16 | 2017-09-20 | Kabushiki Kaisha Toshiba | Active material, nonaqueous electrolyte battery, battery pack, and vehicle |
| CN107369829A (en) * | 2017-06-30 | 2017-11-21 | 陕西科技大学 | A kind of preparation method of lithium ion battery Mao Danzhuan niobium oxide electrode materials |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043441A (en) * | 2022-07-28 | 2022-09-13 | 温州大学碳中和技术创新研究院 | Preparation method of layered oxide positive electrode material based on three-phase heterogeneous symbiotic structure and sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | One dimensional graphene nanoscroll-wrapped MnO nanoparticles for high-performance lithium ion hybrid capacitors | |
| EP3518328B1 (en) | Silicon-containing structure, method of preparing the same, carbon composite using the same, and electrode, lithium battery, and device each including the same | |
| KR101624805B1 (en) | Secondary battery comprising solid electrolyte layer | |
| Yi et al. | Enhanced electrochemical performance of Li-rich low-Co Li1. 2Mn0. 56Ni0. 16Co0. 08− xAlxO2 (0≤ x≤ 0.08) as cathode materials | |
| KR20220092556A (en) | Anode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
| WO2018024184A1 (en) | Method for preparing germanium/graphene/titanium dioxide nanofiber composite material, and battery | |
| CN109659540B (en) | Preparation method of porous carbon-coated antimony telluride nanosheet and application of porous carbon-coated antimony telluride nanosheet as negative electrode material of metal ion battery | |
| CN114050265B (en) | Nickel selenide/manganese selenide nanocomposite loaded by crosslinked nano carbon sheet, preparation method of nickel selenide/manganese selenide nanocomposite and sodium ion battery negative electrode | |
| CN110336003B (en) | Porous silicon-based composite material and preparation method and application thereof | |
| Yin et al. | Hierarchical CuBi 2 O 4 microspheres as lithium-ion battery anodes with superior high-temperature electrochemical performance | |
| JP2020105063A (en) | Doped titanium niobate and battery | |
| Zhang et al. | Chemical replacement route to Cu 2− x Se-coated CuO nanotube array anode for enhanced performance in lithium ion batteries | |
| CN114204002B (en) | Composite coating method of high-compaction high-nickel layered positive electrode material for solid-state battery | |
| Kang et al. | Shape control of hierarchical lithium cobalt oxide using biotemplates for connected nanoparticles | |
| CN111640928A (en) | NCMA quaternary system material, preparation method thereof, lithium battery positive electrode material and lithium battery | |
| CN111115618A (en) | Graphene/carbon/tin oxide nano composite material and preparation method and application thereof | |
| CN113066980B (en) | Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material | |
| Lu et al. | Flexible additive-free CC@ TiO x N y@ SnS 2 nanocomposites with excellent stability and superior rate capability for lithium-ion batteries | |
| CN114242995A (en) | Sodium ion battery nanosheet negative electrode material and preparation method and application thereof | |
| CN110867565B (en) | Preparation method of carbon-coated silicon and zinc oxide composite electrode material | |
| KR20120137809A (en) | Synthesis method of micro-sized and porous lifepo4/c composites by the two-step crystallization process and their application method to cathode materials in li-ion batteries | |
| CN109671920B (en) | Nano-diamond and titanium dioxide hollow sphere composite electrode material and preparation method thereof | |
| Wu et al. | N doped carbon coated V 2 O 5 nanobelt arrays growing on carbon cloth toward enhanced performance cathodes for lithium ion batteries | |
| CN111747449A (en) | Superfine MoO uniformly bridged inside flaky carbon matrix2Electrode material of nano particles and preparation method and application thereof | |
| Wang et al. | Achieving superior high-rate cyclability of LiNi0. 5Mn1. 5O4 cathode material via constructing stable CuO modification interface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |