CN115995537B - Heterojunction MXene modified positive electrode material and preparation method and application thereof - Google Patents
Heterojunction MXene modified positive electrode material and preparation method and application thereof Download PDFInfo
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- CN115995537B CN115995537B CN202211635752.6A CN202211635752A CN115995537B CN 115995537 B CN115995537 B CN 115995537B CN 202211635752 A CN202211635752 A CN 202211635752A CN 115995537 B CN115995537 B CN 115995537B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000012071 phase Substances 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 64
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 53
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 239000007790 solid phase Substances 0.000 claims abstract description 23
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical group 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 66
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 150000003839 salts Chemical class 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 30
- 239000010405 anode material Substances 0.000 claims description 25
- 239000010406 cathode material Substances 0.000 claims description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 13
- 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 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- -1 halide salt Chemical class 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- HHRQHBSHDGPCRL-UHFFFAOYSA-N [O-2].[Mn+2].[Fe+2].[Ni+2].[O-2].[O-2] Chemical compound [O-2].[Mn+2].[Fe+2].[Ni+2].[O-2].[O-2] HHRQHBSHDGPCRL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 3
- 235000014413 iron hydroxide Nutrition 0.000 claims description 3
- CUSDLVIPMHDAFT-UHFFFAOYSA-N iron(3+);manganese(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Fe+3].[Fe+3] CUSDLVIPMHDAFT-UHFFFAOYSA-N 0.000 claims description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- LIJBHSNTSZDMFV-UHFFFAOYSA-L [OH-].[OH-].[Mn].[Ni++] Chemical compound [OH-].[OH-].[Mn].[Ni++] LIJBHSNTSZDMFV-UHFFFAOYSA-L 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 10
- 230000001808 coupling effect Effects 0.000 abstract description 9
- 230000005012 migration Effects 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 9
- 239000011229 interlayer Substances 0.000 abstract description 6
- 230000002427 irreversible effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 229910018416 Mn0.33O2 Inorganic materials 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 14
- 239000010410 layer Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229940062993 ferrous oxalate Drugs 0.000 description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001778 solid-state sintering Methods 0.000 description 3
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910018970 NaNi0.5Mn0.5O2 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 2
- 229910009846 Ti4AlN3 Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000032683 aging 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 230000035882 stress Effects 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003466 welding Methods 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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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a heterojunction MXene modified positive electrode material, a preparation method and application thereof, wherein the modified positive electrode material is obtained by solid-phase sintering of MXene and a sodium ion battery O3 phase layered oxide positive electrode material, the MXene is M n+1XnTx, wherein M is transition metal, X is C and/or N element, T represents surface end sealing group, the O3 phase layered oxide positive electrode material is NaNi aFebMncO2, a, b and C are more than or equal to 0 and less than or equal to 1, and a+b+c=1. The invention utilizes MXene to form a composite material with a heterojunction structure through solid phase sintering and O3 phase layered oxide, has strong coupling effect at a heterojunction interface, and can anchor NaNi aFebMncO2 so as to inhibit irreversible phase change reaction; meanwhile, interface electron transfer can be promoted, conductivity is improved, and the introduction of MXene increases the interlayer spacing of the O3 phase layered oxide material and accelerates Na + migration kinetics. The heterojunction MXene modified O3 phase layered oxide positive electrode material can effectively solve the problems of low capacity and poor cycling stability of a sodium ion battery.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a heterojunction MXene modified positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries are widely used in the field of energy devices, but since the existing lithium elements on earth are very limited, it is necessary to develop energy storage devices based on other carriers to solve the above problems. The sodium resources are rich, the cost is low, and the physical and chemical properties of the sodium ion battery are similar to those of the lithium ion battery, so that the requirement of future energy storage is hopeful to be met. However, since the relative molecular weight of sodium is higher than that of lithium, the radius of sodium ion is also larger than that of lithium ion, so that it is difficult to insert or extract sodium ions from the layered cathode material, and thus the energy density of sodium ion battery is lower than that of lithium ion battery, which greatly hinders the commercialization of sodium ion battery. Since the theoretical density of the positive electrode material in the sodium ion battery is the upper limit of the energy density of the battery core, the power density of the sodium ion battery is usually improved by improving the capacity of the positive electrode material for containing sodium ions and the smoothness of a transmission channel, so that the development of the positive electrode material with high performance is the problem which needs to be solved in the trend of the sodium ion battery.
Among various positive electrode materials of sodium ion batteries, O3-phase layered oxides are receiving attention because of their advantages of providing sufficient sodium in a full battery, high electrochemical activity, high theoretical specific capacity, and ease of synthesis. However, the problems of complex irreversible phase change, large volume change, high Na + migration energy barrier and the like limit the practical application of the O3 phase layered oxide. Improving the performance of the O3 phase layered oxide by doping heterogeneous elements is one of the commonly used methods, but its improving effect is limited. For example, wang et Al prepared Al-doped NaAl 0.02Ni0.49Mn0.49O2 material (HONG N,WU K,PENG Z,et al.Improved high rate performance and cycle performance of Al-doped O3-type NaNi0.5Mn0.5O2 cathode materials for sodium-ion batteries[J].Journal of Physical Chemistry C,2020,124(42):22925-22933.). using a sol-gel method had a capacity retention of 63.2% after 200 cycles of 2mol% Al-doped material at a current density of 240 mAg -1, which is 21.4% higher than NaNi 0.5Mn0.5O2. Although gram capacity and cycle performance of the Al-doped NaAl 0.02Ni0.49Mn0.49O2 material are improved, the problem of phase change is not well improved, so that the cycle performance is still poor.
Therefore, how to inhibit irreversible phase change and volume change of the layered positive electrode material of the O3 type sodium ion battery, reduce the migration energy barrier of Na + and improve the migration rate of sodium ions becomes one of the key problems in the related technology of the sodium ion battery.
Disclosure of Invention
The invention aims to solve the technical problem of providing a heterojunction MXene modified positive electrode material, a preparation method and application thereof, wherein MXene with abundant functional groups on the surface is adopted to be compounded with an O3 phase layered oxide positive electrode material in a solid phase sintering mode, so as to obtain the MXene modified positive electrode material with a heterojunction structure. The heterogeneous interface of MXene and the O3 phase layered oxide positive electrode material has strong electron coupling effect, and the O3 phase layered oxide positive electrode material can be anchored, so that the occurrence of reversible phase transformation reaction is inhibited; meanwhile, the strong electron coupling effect at the interface can promote electron transfer at the interface, and the introduction of MXene increases the interlayer spacing of the O3 phase layered oxide anode material, reduces the Na + migration energy barrier and is beneficial to the improvement of Na + migration rate.
In order to solve the technical problems, the invention provides the following technical scheme:
The first aspect of the invention provides a preparation method of a heterojunction MXene modified anode material, which comprises the steps of uniformly mixing the MXene material with a sodium ion battery O3 phase layered oxide anode material, and preparing the heterojunction MXene modified anode material through solid phase sintering;
The MXene is M n+1XnTx, wherein N is any integer from 1 to 3, X is more than 0, M is transition metal Sc, ti, V, cr, Y, zr, nb, mo, hf, ta, W, ni, fe, mn or Zn, X is C and/or N element, T is surface end capping group, and the end capping group comprises-OH, -O-and-F.
Further, the O3 phase layered oxide positive electrode material of the sodium ion battery is NaNi aFebMncO2, a, b and c are not less than 0 and not more than 1, and a+b+c=1.
Further, the MXene is Ti3C2Tx、Ti4N3Tx、Ni3N2Tx、Zr3C2Tx、Ta5N4Tx、V3N2Tx、Fe2NTx、Mn3C2Tx or Zn 4C3Tx, more preferably Ti 3C2Tx.
Further, the MXene material and the sodium ion battery O3 phase layered oxide anode material are uniformly mixed by ball milling.
Further, in the step of solid phase sintering: the temperature rising rate is 0.01-10 ℃/min, the solid phase sintering temperature is 700-1200 ℃, and the heat preservation time after solid phase sintering is 0.5-48 h.
The invention utilizes the abundant functional groups on the surface of the two-dimensional MXene material to anchor the transition metal element of the O3 layered oxide, and the partial MXene intercalated composite anode material is obtained through solid phase sintering, as the MXene material and the O3 layered oxide material have different energy band gaps, a heterojunction structure is formed at the interface of the two materials, the energy level transition of electrons occurs at the heterojunction to form an electric field, the strong coupling effect is shown, the rapid transfer of interface electrons can be promoted, and the charge transfer performance of the anode material is optimized; meanwhile, the interlayer spacing of the O3 phase layered material is widened due to the insertion of the two-dimensional MXene material.
Further, the preparation method of the MXene material comprises the following steps:
(1) Uniformly mixing the MAX phase and the halide salt in a molar ratio of 1-10:1-9, and annealing for 0.5-10 h at 450-1150 ℃;
(2) And washing the annealed product by adopting hydrofluoric acid, and then washing by water and freeze-drying to obtain the MXene heterojunction.
Further, in the step (1), the MAX phase is one of Ti3AlC2、Ti4AlN3、Ni3AlN2、Zr3AlC2、Fe2AlN、Ta5AlN4、V3AlN2、Zn4AlC3 and the like; the halide salt may be NaCl, KCl, naF, preferably NaF.
Further, in the step (2), the concentration of the hydrofluoric acid is 1wt% to 15wt%.
Further, the preparation of the sodium ion battery O3 phase layered oxide positive electrode material comprises the following steps: and weighing metal salt corresponding to the O3 phase layered oxide anode material of the sodium ion battery according to a certain molar ratio, uniformly mixing, heating to 700-1200 ℃ at a heating rate of 0.01-10 ℃/min, and preserving heat for 0.5-48 h to obtain the O3 phase layered oxide anode material.
Further, the metal salt comprises sodium salt and metal salts of other metal elements in the O3 phase layered oxide positive electrode material, or comprises sodium salt and precursor metal salt, wherein the metal elements in the precursor metal salt are other metal elements except sodium in the O3 phase layered oxide positive electrode material of the sodium ion battery.
Further, the sodium salt is one or more of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate.
Further, the metal salts of the other metal elements include one or more of nickel-containing salts, iron-containing salts, and manganese-containing salts.
Further, the nickel-containing salt is one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide, nickel carbonyl and nickel oxide.
Further, the iron-containing salt is one or more of ferric oxide, ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate.
Further, the manganese-containing salt is one or more of potassium permanganate, potassium manganate and manganese oxide.
Further, the precursor metal salt is one or more of nickel oxide, nickel iron manganese oxide, iron oxide, manganese iron oxide, nickel manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron manganese hydroxide and nickel manganese hydroxide.
Further, metal salts corresponding to the O3 phase layered oxide positive electrode material of the sodium ion battery are weighed according to the molar ratio of each metal element in the positive electrode material, wherein the sodium salt content is slightly larger than the required molar amount, so as to compensate the loss of the sodium content in the sintering process. For example, when the positive electrode material is NaNi 0.34Fe0.33Mn0.33O2, the metal salt may be sodium hydroxide, nickel oxide, ferrous oxide, or manganese oxide, and the molar ratio of sodium hydroxide, nickel oxide, ferrous oxide, or manganese oxide is preferably 1-1.1:0.34:0.33:0.33.
The second aspect of the invention provides a heterojunction MXene modified cathode material, wherein MXene is M n+1XnTx, N is any integer from 1 to 3, X is more than 0, M is transition metal Sc, ti, V, cr, Y, zr, nb, mo, hf, ta, W, ni, fe, mn or Zn, X is C and/or N element, T is a surface end-capping group, and the end-capping group comprises-OH, -O-and-F; the positive electrode material is a sodium ion battery O3 phase layered oxide positive electrode material.
Further, the particle size of the heterojunction MXene modified positive electrode material is 0.54-67.5 mu m, the specific surface area is 0.25m 2/g～45.7m2/g, and the water content is 0.02-2.69%.
The third aspect of the invention provides a positive electrode plate, which comprises the heterojunction MXene modified positive electrode material prepared by the preparation method of the first aspect and/or the heterojunction MXene modified positive electrode material of the second aspect.
According to a fourth aspect of the invention, there is provided a sodium battery comprising the positive electrode sheet of the third aspect.
Compared with the prior art, the invention has the beneficial effects that:
1. The MXene material and the O3 phase layered oxide positive electrode material are compounded in a solid phase sintering mode, so that the MXene modified positive electrode material with a heterojunction structure is prepared, the MXene with rich functional groups and the O3 phase layered oxide positive electrode material are tightly combined, a strong coupling effect is shown at a heterogeneous interface of the MXene with the O3 phase layered oxide positive electrode material, on one hand, the O3 phase layered oxide positive electrode material can be anchored by the MXene material through the strong coupling effect, the large-volume stress of the O3 phase layered oxide positive electrode material can be released quickly, the problem of pulverization caused by irreversible phase change of the material in a circulating process is prevented, and the circulating stability of the battery is improved; on the other hand, the strong electron coupling effect at the heterogeneous interface has an ultrafast charge separation process, and can promote the rapid transfer of interface electrons, so that the charge transfer dynamics of the anode material is optimized.
2. The MXene modified positive electrode material with the heterojunction structure, which is prepared by the invention, has the advantages that the introduction of MXene increases the interval between the interface layers of the O3 phase layered oxide positive electrode material, the expansion of the interval between the layers can greatly reduce the transmission resistance of sodium ions between the layers, and the migration rate of the sodium ions is accelerated, so that the electrochemical performance of a sodium ion battery is improved.
3. According to the invention, MXene is introduced between interface layers of the O3-phase layered oxide anode material, and a heterojunction structure is formed at the interface of the MXene and the O3-phase layered oxide anode material, so that the charge transfer dynamics and the cycle stability of the O3-phase layered oxide anode material are greatly optimized; compared with the non-modified O3 phase layered oxide positive electrode material, the sodium ion battery containing the MXene modified positive electrode material with the heterojunction structure has the advantages that the discharge specific capacity is improved by 31.3% under the current density of 0.1 ℃, the initial coulombic efficiency is up to 86.13%, the capacity retention rate after 100 times of circulation is 94.6%, the capacity retention rate after 500 times of circulation is 85.2%, the capacity retention rate after 1000 times of circulation is 76.3%, and the high gram capacity and excellent circulation stability are shown.
Drawings
FIG. 1 is a graph showing the results of ICP testing of NaNi 0.34Fe0.33Mn0.33O2 materials prepared in example 1;
FIG. 2 is a scanning electron microscope image of NaNi 0.34Fe0.33Mn0.33O2 materials prepared in example 1;
FIG. 3 is a scanning electron microscope image of the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 material prepared in example 1;
FIG. 4 is a transmission electron microscope image of the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 material prepared in example 1;
FIG. 5 is a TEM MAPPING diagram of the elements Ti and C in the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 material prepared in example 1;
FIG. 6 is an XRD overlay of the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 material prepared in example 1 and an O3 phase standard PDF card;
Fig. 7 is an XRD overlay of NaNi 0.34Fe0.33Mn0.33O2 material prepared in example 1 with standard PDF card in O3 phase.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
As described in the background art, in various positive electrode materials of sodium ion batteries, the O3 phase layered oxide positive electrode material has the advantages of high sodium content, high electrochemical activity, high theoretical specific capacity and the like, but when the material is used as the positive electrode material of sodium ion batteries, the problems of complex irreversible phase change, large volume change, high Na + migration energy barrier and the like exist, and the practical application of the O3 phase layered oxide is severely limited. At present, the O3 phase layered oxide is modified by means of element doping, cladding and the like, but the improvement effect is limited, and the capacity and the cycle performance are difficult to be compatible.
The research shows that the surface of MXene has rich functional groups, strong polarity and excellent charge distribution regulating capability, and the performance of the obtained modified sodium ion positive electrode material is not obviously improved although the two-dimensional MXene which has high conductivity, low ion diffusion barrier and easy dispersion is compounded with the sodium ion positive electrode material through a hydrothermal or ultrasonic mode at present.
In order to solve the technical problems, the invention provides a preparation method of a heterojunction MXene modified anode material, which is characterized in that the MXene material and a sodium ion battery O3 phase layered oxide anode material are uniformly mixed, and the heterojunction MXene modified anode material is prepared through solid phase sintering. Wherein the MXene material is M n+1XnTx, N is any integer from 1 to 3, X is more than 0, M is preferably Sc, ti, V, cr, Y, zr, nb, mo, hf, ta, W, ni, fe, mn or Zn, X is C and/or N element, T is surface end capping group, and the end capping group comprises-OH, -O-and-F.
In some preferred embodiments, the sodium ion battery O3 phase layered oxide cathode material is NaNi aFebMncO2, 0.ltoreq.a, b, c.ltoreq.1, a+b+c=1, e.g., naNi 0.34Fe0.33Mn0.33O2.
Unlike available technology, which adopts hydrothermal or ultrasonic mode to physically mix MXene and sodium ion anode material, the present invention adopts solid phase sintering process to compound MXene and O3 phase layered oxide anode material structurally, and the two materials are fused together to form hetero structure in the interface between O3 phase layered oxide material and part of two-dimensional MXene material. As the MXene surface has rich functional groups, the MXene surface can be tightly combined with the O3 phase layered oxide positive electrode material through solid phase sintering, and has strong coupling effect at the interface, the O3 phase layered oxide positive electrode material can be anchored through the strong coupling effect, and the irreversible phase change of the material in the circulation process is inhibited, so that the circulation stability of the battery is improved; in addition, the introduction of MXene increases the interval of the interface layers of the O3 phase layered oxide anode material, reduces the transmission resistance of sodium ions between the layers, thereby accelerating the migration rate of the sodium ions and further greatly optimizing the charge transfer kinetics of the O3 phase layered oxide anode material.
In some preferred embodiments, the MXene is Ti3C2Tx、Ti4N3Tx、Ni3N2Tx、Zr3C2Tx、Ta5N4Tx、V3N2Tx、Fe2NTx、Mn3C2Tx or Zn 4C3Tx, more preferably Ti 3C2Tx.
In some preferred embodiments, the MXene material is mixed uniformly with the sodium ion battery O3 phase layered oxide cathode material by ball milling such that the two react sufficiently and uniformly at the temperature of solid phase sintering. In the step of solid phase sintering, the following steps are adopted: the temperature rising rate is 0.01-10 ℃/min, the solid phase sintering temperature is 700-1200 ℃, and the heat preservation time after solid phase sintering is 0.5-48 h. For example: raising the temperature to 1050 ℃ at the temperature raising rate of 3.5 ℃/min, and preserving the heat for 13h.
In some preferred embodiments, the MXene material is prepared by a preparation method comprising the steps of:
(1) Uniformly mixing the MAX phase and the halide salt in a molar ratio of 1-10:1-9, and annealing for 0.5-10 h at 450-1150 ℃;
(2) And washing the annealed product by adopting hydrofluoric acid, and then washing by water and freeze-drying to obtain the MXene heterojunction.
In some preferred embodiments, the MAX phase in step (1) is one of Ti3AlC2、Ti4AlN3、Ni3AlN2、Zr3AlC2、Fe2AlN、Ta5AlN4、V3AlN2、Zn4AlC3, etc.; the halide salt may be NaCl, KCl, naF, preferably NaF.
In some preferred embodiments, the concentration of hydrofluoric acid in step (2) is 1wt% to 15wt%, e.g., 5wt%, 10wt%, not limited to the recited concentrations.
In some preferred embodiments, the preparation of the sodium ion battery O3 phase layered oxide cathode material comprises the steps of: and weighing metal salt corresponding to the O3 phase layered oxide anode material of the sodium ion battery according to a certain molar ratio, uniformly mixing, heating to 700-1200 ℃ at a heating rate of 0.01-10 ℃/min, and preserving heat for 0.5-48 h to obtain the O3 phase layered oxide anode material.
In some preferred embodiments, the metal salt includes a sodium salt and a metal salt of each other metal element in the O3 phase layered oxide cathode material, wherein the metal salt of each other metal element is one or more of a nickel-containing salt, a ferric salt, and a manganese-containing salt, the nickel-containing salt may be one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide, nickel carbonyl, and nickel oxide, the ferric salt may be one or more of iron oxide, ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate, and ferrous oxalate, and the manganese-containing salt may be one or more of potassium permanganate, potassium manganate, and manganese oxide.
The metal salt more preferably includes a sodium salt and a precursor metal salt, wherein the metal element in the precursor metal salt is other metal elements except sodium in the sodium ion battery O3 phase layered oxide positive electrode material, and can be selected from one of nickel oxide, nickel iron manganese oxide, iron oxide, manganese iron oxide, nickel manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron manganese hydroxide and nickel manganese hydroxide; for example, when the O3 phase layered oxide cathode material is NaNi 0.34Fe0.33Mn0.33O2, the precursor metal salt is preferably nickel iron manganese hydroxide or nickel iron manganese oxide.
In some preferred embodiments, the metal salt corresponding to the sodium ion battery O3 phase layered oxide positive electrode material is weighed according to the molar ratio of each metal element in the positive electrode material, wherein the sodium salt content is slightly greater than the required molar amount to compensate for the loss of sodium content in the sintering process. For example, when the positive electrode material is NaNi 0.34Fe0.33Mn0.33O2, the metal salt may be sodium hydroxide, nickel oxide, ferrous oxide, or manganese oxide, and the molar ratio of sodium hydroxide, nickel oxide, ferrous oxide, or manganese oxide is preferably 1-1.1:0.34:0.33:0.33.
The invention also provides a heterojunction MXene modified anode material, wherein MXene is M n+1XnTx, N is any integer of 1-3, X is more than 0, M is transition metal Sc, ti, V, cr, Y, zr, nb, mo, hf, ta, W, ni, fe, mn or Zn, X is C and/or N element, T is a surface end sealing group, and the end sealing group comprises-OH, -O-and-F; the positive electrode material is a sodium ion battery O3 phase layered oxide positive electrode material.
In some preferred embodiments, the heterojunction MXene modified cathode material has a particle size of 0.54 μm to 67.5 μm, a specific surface area of 0.25m 2/g～45.7m2/g, and a water content of 0.02% to 2.69%.
In addition, the invention also provides a positive electrode plate, which comprises the heterojunction MXene modified positive electrode material and/or the heterojunction MXene modified positive electrode material prepared by the preparation method.
The invention also provides a sodium battery, which comprises the positive pole piece.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
The embodiment relates to preparation of a heterojunction MXene modified positive electrode material (Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2), which comprises the following specific operations:
(1) Adding nickel hydroxide iron manganese and sodium carbonate into a reaction vessel according to a molar ratio of 1:0.55, stirring and mixing uniformly, heating to 1050 ℃ at a speed of 3.5 ℃/min, and carrying out solid-state sintering treatment for 13h to obtain NaNi 0.34Fe0.33Mn0.33O2 powder;
(2) Mixing Ti 3AlC2 and NaF in a molar ratio of 1:6.3, and annealing at 550 ℃ for 5.5 hours; after the annealing process is completed, washing the product with deionized water and collecting the product by centrifugation, then washing the product with 5wt% HF for 2 hours to remove metal impurities, washing the product with deionized water and freeze-drying the product to obtain a Ti 3C2Tx material;
(3) And (3) ball-milling and uniformly mixing the NaNi 0.34Fe0.33Mn0.33O2 powder and the Ti 3C2Tx material, transferring the mixture into a sintering furnace, heating to 900 ℃ at a heating rate of 6 ℃/min, and carrying out solid-state sintering treatment for 8 hours to obtain the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 powder.
The ICP test results (shown in fig. 1) of NaNi 0.34Fe0.33Mn0.33O2 prepared in this example are as follows: na:1, ni:0.34, fe:0.33, mn:0.34.
Scanning Electron Microscope (SEM), transmission Electron Microscope (TEM) and X-ray diffraction (XRD) characterization were performed on NaNi 0.34Fe0.33Mn0.33O2 and Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 materials prepared in this example, and the characterization results are shown below:
Fig. 2 and 3 are SEM images of NaNi 0.34Fe0.33Mn0.33O2 and Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 materials, respectively, and it is apparent from the figures that the interlayer spacing of the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 material increases.
FIG. 4 is a TEM image of a Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 material from which the embedded layer and a small amount of Ti 3C2Tx distributed on the surface can be observed, and from which the lattice fringes attributed to the Ti 3C2Tx (004) crystal plane can be observed in a high-resolution TEM image; fig. 5 is a TEM MAPPING diagram of Ti and C elements in Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2, where dark color is interlayer gaps, light color is material surface, and in combination with the distribution of lattice fringes in fig. 4, ti 3C2Tx material is distributed on the surface and interlayer of the composite material.
FIGS. 6 and 7 show XRD stacks of Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 and pure NaNi 0.34Fe0.33Mn0.33O2 materials, respectively, and an O3 phase standard PDF card, where it is seen that both Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 and pure NaNi 0.34Fe0.33Mn0.33O2 materials are O3 phase layered oxide materials, but that the diffraction peaks of Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 are shifted (shown in FIG. 6) due to the fact that part of MXene enters the layers of the O3 phase layered oxide materials, and that a hetero peak attributed to MXene occurs between 10 and 35 degrees in 2 theta, which further illustrates the inclusion of MXene materials in the composite.
Example 2
The present example relates to the preparation of a heterojunction MXene modified cathode material (Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2), which differs from example 1 only in the preparation process of step (1) NaNi 0.34Fe0.33Mn0.33O2, specifically as follows:
(1) Adding sodium carbonate, nickel nitrate, ferrous oxalate and manganese oxide into a reaction vessel according to the molar ratio of 0.55:0.34:0.33:0.33, stirring and mixing uniformly, heating to 1050 ℃ at 3.5 ℃/min, and preserving heat for 13h to perform solid-state sintering treatment to obtain NaNi 0.34Fe0.33Mn0.33O2 powder.
Steps (2) and (3) were identical to example 1.
Example 3
Compared with the example 1, ti 4N3Tx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material Ti 4N3Tx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Example 4
Compared with the example 2, ti 4N3Tx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material Ti 4N3Tx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Example 5
Compared with the example 1, ni 3N2Tx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material Ni 3N2Tx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Example 6
Compared with the example 1, zr 3C2Tx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material Zr 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Example 7
Compared with the example 1, ta 5N4Tx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material Ta 5N4Tx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Example 8
Compared with the example 1, V 3N2Tx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material V 3N2Tx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Example 9
Compared with the example 1, fe 2NTx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material Fe 2NTx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Example 10
Compared with the example 1, mn 3C2Tx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material Mn 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Example 11
Compared with the example 1, zn 4C3Tx is adopted to replace the Ti 3C2Tx material prepared in the step (2), and the rest steps are the same, so that the heterojunction MXene modified cathode material Zn 4C3Tx/NaNi0.34Fe0.33Mn0.33O2 is prepared.
Comparative example 1
The preparation method in example 1 was used to prepare the O3 phase layered oxide NaNi 0.34Fe0.33Mn0.33O2 in this comparative example.
Comparative example 2
The comparative example adopts an ultrasonic method to prepare Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 composite material, and the comparative example is different from the example 1 only in the step (3), and the specific operation is as follows:
Steps (1), (2) are consistent with example 1;
(3) And placing NaNi 0.34Fe0.33Mn0.33O2 powder and the Ti 3C2Tx material into an ultrasonic instrument for ultrasonic treatment for 8 hours, and vacuum drying and sintering at 70 ℃ for 8 hours to obtain the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 composite material.
Comparative example 3
The comparative example adopts a hydrothermal method to prepare Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 composite material, and the difference from the example 1 is only in the step (3), and the specific operation is as follows:
Steps (1), (2) are consistent with example 1;
(3) And uniformly mixing NaNi 0.34Fe0.33Mn0.33O2 powder with the Ti 3C2Tx material, placing the mixture in a hydrothermal kettle, and transferring the mixture into a hydrothermal furnace to keep the temperature at 220 ℃ for 8 hours to obtain the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 composite material.
Application and performance characterization
1. Assembly of soft package battery core
Preparation of a positive plate: the materials prepared in the examples and the comparative examples are respectively used as positive electrode active substances to prepare positive electrode plates, the positive electrode active substances, conductive carbon and PVDF are dissolved in N-methyl pyrrolidone according to the mass ratio of 90:5:5, and the positive electrode plates are obtained by coating, drying and cutting the materials after uniform stirring.
Preparing a negative plate: and dissolving the anode hard carbon material, the conductive carbon and the CMC/SBR binder in water according to a ratio of 85:10:5, uniformly stirring, and then coating, drying and cutting to obtain the anode sheet.
Preparation of electrolyte: 1M sodium hexafluorophosphate is adopted to dissolve in a solution of ethylene carbonate and propylene carbonate plus 5 percent fluoroethylene carbonate in a volume ratio of 1:1, so as to obtain electrolyte.
The pole piece adopts a winding process, the diaphragm is firstly wound for 5/6 circles, then the anode and the cathode are sequentially wound for 8 circles, and finally the anode is wound, so that the cathode piece is completely wrapped in the anode. And welding the prepared winding core with the tab, pasting the tab, sealing the winding core with an aluminum plastic film, baking the winding core in a vacuum oven for 40-120 hours, taking out the winding core, testing the water content (H 2 O is required to be less than 200 ppm), and then injecting liquid according to a certain liquid injection coefficient and proportion, sealing, aging, forming and capacity-dividing testing.
2. Performance testing
The assembled battery is placed on a blue standard tester for 8 hours, and then starts to test, and is charged and discharged at a rate of 0.1C, wherein the theoretical specific capacity is 130/370mAh/g (the capacity is designed according to the pre-calculation). And charging and discharging at first by adopting a current of 0.1C, and finally, reading and calculating a corresponding capacity value.
The initial specific capacity of each battery in the voltage interval of 2-4V, the initial coulombic efficiency and the discharge specific capacity of 100/300/500/1000 cycles are tested, and the test results are summarized in the following table 1:
Table 1 shows the performance of sodium ion batteries prepared from the positive electrode materials of examples 1 to 11 and comparative examples 1 to 3
From the above table, it is understood that in examples 1 to 11, MXene was introduced into NaNi 0.34Fe0.33Mn0.33O2 material by solid phase sintering, which effectively improved the discharge specific capacity, initial coulombic efficiency and cycle stability of the sodium ion battery, as compared with the unmodified NaNi 0.34Fe0.33Mn0.33O2 material of comparative example 1. Wherein, the electrochemical performance of the sodium ion battery prepared by taking Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 prepared in example 1 as the positive electrode active material is better, the initial specific capacity of 140.2mA h/g is realized, which is improved by 31.3 percent compared with comparative example 1, the capacity retention rate after 500 circles is 85.2 percent, the capacity retention rate after 1000 circles is still as high as 76.3 percent, and the capacity retention rate of the corresponding sodium ion battery in comparative example 1 after 1000 circles is only 66.9 percent.
In addition, compared with unmodified NaNi 0.34Fe0.33Mn0.33O2, the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 composite material prepared by an ultrasonic method (comparative example 2) or a hydrothermal method (comparative example 3) has improved initial specific capacity, initial coulomb efficiency and cycle stability, but the effect is poor, which is far lower than that of the Ti 3C2Tx/NaNi0.34Fe0.33Mn0.33O2 composite material with the heterojunction structure prepared by solid-phase sintering in example 1, and the invention also shows that the initial specific capacity and cycle stability of the sodium ion battery can be greatly improved by introducing MXene into the O3 phase layered oxide material by the solid-phase sintering method and forming the heterojunction structure, and the initial coulomb efficiency lost by the whole battery is compensated.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (8)
1. The preparation method of the heterojunction MXene modified positive electrode material is characterized in that the MXene material and a sodium ion battery O3 phase layered oxide positive electrode material are uniformly mixed, and the heterojunction MXene modified positive electrode material is prepared through solid phase sintering;
The MXene is M n+1XnTx, wherein N is any integer of 1-3, X is more than 0, M is transition metal Sc, ti, V, cr, Y, zr, nb, mo, hf, ta, W, ni, fe, mn or Zn, X is C and/or N element, T is surface end sealing group, and the end sealing group comprises-OH, -O-and-F;
The O3 phase layered oxide positive electrode material of the sodium ion battery is NaNi aFebMncO2, 0<a, b and c are less than 1, and a+b+c=1;
The solid phase sintering step comprises the following steps: the temperature rising rate is 0.01-10 ℃/min, the solid phase sintering temperature is 700-1200 ℃, and the heat preservation time after solid phase sintering is 0.5-48 h;
The preparation of the MXene material comprises the following steps:
(1) Uniformly mixing the MAX phase and the halide salt in a molar ratio of 1-10:1-9, and annealing at 450-1150 ℃ for 0.5-10 h;
(2) Washing the annealed product by adopting hydrofluoric acid, washing by water and freeze-drying to obtain the MXene material;
The preparation of the sodium ion battery O3 phase layered oxide positive electrode material comprises the following steps: and weighing metal salts corresponding to the O3 phase layered oxide anode material of the sodium ion battery according to a certain molar ratio, uniformly mixing, heating to 700-1200 ℃ at a heating rate of 0.01-10 ℃/min, and preserving heat for 0.5-48 h to obtain the O3 phase layered oxide anode material.
2. The method of claim 1, wherein the MXene is Ti3C2Tx、Ti4N3Tx、Ni3N2Tx、Zr3C2Tx、Ta5N4Tx、V3N2Tx、Fe2NTx、Mn3C2Tx or Zn 4C3Tx.
3. The method according to claim 1, wherein the metal salt comprises sodium salt and a precursor metal salt, and the metal element in the precursor metal salt is other metal elements except sodium in the O3-phase layered oxide cathode material of the sodium ion battery.
4. The method according to claim 3, wherein the sodium salt is one or more of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate, and sodium phenolate; the precursor metal salt is a plurality of nickel oxide, nickel iron manganese oxide, iron oxide, manganese iron oxide, nickel manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel hydroxide iron manganese, nickel hydroxide manganese.
5. A heterojunction MXene modified cathode material prepared by the method of any one of claims 1-4.
6. The heterojunction MXene modified cathode material according to claim 5, wherein the particle size of the heterojunction MXene modified cathode material is 0.54-67.5 μm, the specific surface area is 0.25 m 2/g~45.7 m2/g, and the water content is 0.02-2.69%.
7. The positive electrode plate is characterized by comprising the heterojunction MXene modified positive electrode material prepared by the preparation method of any one of claims 1-4 or the heterojunction MXene modified positive electrode material of claim 6.
8. A sodium battery comprising the positive electrode sheet of claim 7.
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| CN114373917A (en) * | 2022-01-18 | 2022-04-19 | 山东大学 | Sodium-ion battery positive electrode composite material and preparation method and application thereof |
| CN114604896A (en) * | 2022-03-25 | 2022-06-10 | 中南大学 | MXene composite modified binary manganese-based sodium electro-precursor and preparation method thereof |
| CN114843469A (en) * | 2022-05-07 | 2022-08-02 | 广西师范大学 | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium-ion battery positive electrode material and preparation method thereof |
| CN115057485A (en) * | 2022-06-17 | 2022-09-16 | 中国科学技术大学 | Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof |
| CN115207339A (en) * | 2022-08-25 | 2022-10-18 | 江苏正力新能电池技术有限公司 | Positive electrode material, preparation method thereof, positive electrode piece and O3-type layered sodium-ion battery |
| CN115425196A (en) * | 2022-08-30 | 2022-12-02 | 山东大学 | Oxide-coated sodium battery positive electrode material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114373917A (en) * | 2022-01-18 | 2022-04-19 | 山东大学 | Sodium-ion battery positive electrode composite material and preparation method and application thereof |
| CN114604896A (en) * | 2022-03-25 | 2022-06-10 | 中南大学 | MXene composite modified binary manganese-based sodium electro-precursor and preparation method thereof |
| CN114843469A (en) * | 2022-05-07 | 2022-08-02 | 广西师范大学 | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium-ion battery positive electrode material and preparation method thereof |
| CN115057485A (en) * | 2022-06-17 | 2022-09-16 | 中国科学技术大学 | Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof |
| CN115207339A (en) * | 2022-08-25 | 2022-10-18 | 江苏正力新能电池技术有限公司 | Positive electrode material, preparation method thereof, positive electrode piece and O3-type layered sodium-ion battery |
| CN115425196A (en) * | 2022-08-30 | 2022-12-02 | 山东大学 | Oxide-coated sodium battery positive electrode material and preparation method and application thereof |
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