CN115954463A - Sodium ion battery layered oxide composite material and preparation method thereof, positive plate and sodium ion battery - Google Patents
Sodium ion battery layered oxide composite material and preparation method thereof, positive plate and sodium ion battery Download PDFInfo
- Publication number
- CN115954463A CN115954463A CN202310220632.8A CN202310220632A CN115954463A CN 115954463 A CN115954463 A CN 115954463A CN 202310220632 A CN202310220632 A CN 202310220632A CN 115954463 A CN115954463 A CN 115954463A
- Authority
- CN
- China
- Prior art keywords
- sodium
- ion battery
- composite material
- nickel
- layered oxide
- Prior art date
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 69
- 239000000843 powder Substances 0.000 claims description 56
- 239000011734 sodium Substances 0.000 claims description 36
- 235000002639 sodium chloride Nutrition 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 27
- 159000000000 sodium salts Chemical class 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 238000001192 hot extrusion Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 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 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 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 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 235000011008 sodium phosphates Nutrition 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- 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 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- 235000014413 iron hydroxide Nutrition 0.000 claims description 3
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 claims description 3
- KEBVLXZBNYKBFW-UHFFFAOYSA-J iron(2+);manganese(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Fe+2] KEBVLXZBNYKBFW-UHFFFAOYSA-J 0.000 claims description 3
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 claims description 3
- 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 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
- 229910000360 iron(III) sulfate Inorganic materials 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
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 3
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 description 25
- 239000012071 phase Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 244000241872 Lycium chinense Species 0.000 description 10
- 235000015468 Lycium chinense Nutrition 0.000 description 10
- 235000013399 edible fruits Nutrition 0.000 description 10
- -1 polyethylene Polymers 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 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 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910021260 NaFe Inorganic materials 0.000 description 2
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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Images
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- 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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Abstract
The invention discloses a sodium ion battery layered oxide composite material with a molecular formula of M x B y /NaNi a Fe b Mn c O 2 Wherein: m is an alkali metal element, x is more than or equal to 1, and y is less than or equal to 9;0 ≦ a, b, c ≦ 1, and a + b + c =1. The invention also discloses a preparation method of the layered oxide composite material for the sodium ion battery, and a positive plate and the sodium ion battery prepared from the layered oxide composite material. Sodium ion battery layer of the inventionThe layered oxide composite material can improve the high-temperature stability of the layered oxide and improve the high-temperature cycle performance and capacity of the sodium-ion battery.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a layered oxide composite material of a sodium ion battery, a preparation method of the layered oxide composite material, a positive plate and the sodium ion battery.
Background
Among various cathode materials for sodium ion batteries, O3 phase layered oxides have received much attention due to their advantages of sufficient sodium in the full cell, high electrochemical activity, high theoretical specific capacity, and easy synthesis. However, the problems of low energy density and poor high temperature stability limit the practical application of the O3 phase layered oxide.
Therefore, how to improve the high-temperature cycle performance and energy density of the O3 phase layered oxide cathode material becomes one of the key problems in the related art of the sodium ion battery.
Disclosure of Invention
The invention aims to provide a layered oxide composite material for a sodium ion battery, so as to improve the high-temperature stability of the layered oxide and improve the high-temperature cycle performance and capacity of the sodium ion battery.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a sodium-ion battery layered oxide composite material, wherein the molecular formula of the sodium-ion battery layered oxide composite material is M x B y /NaNi a Fe b Mn c O 2 Wherein: m is an alkali metal element, x is more than or equal to 1, and y is less than or equal to 9;0 ≦ a, b, c ≦ 1, and a + b + c =1.
Further, the D50 particle size of the sodium-ion battery layered oxide composite material is 0.01-25.5 μm;
and/or the specific surface area of the layered oxide composite material of the sodium-ion battery is 0.01-47.4 m 2 /g；
And/or the water content of the layered oxide composite material of the sodium-ion battery is 0.01-1.25%.
The invention provides a preparation method of a layered oxide composite material of a sodium-ion battery, which comprises the following steps:
s1, mixing alkali metal M powder and boron powder in vacuum or inert atmosphere, and performing vacuum hot extrusion to obtain M x B y A compound;
s2, mixing M x B y Compound, naNi a Fe b Mn c O 2 After the powder is mixed, carrying out hot extrusion to obtain the layered oxide composite material of the sodium-ion battery;
wherein, in the step S1, x is more than or equal to 1, and y is less than or equal to 9;
in step S2, 0 is equal to or less than a, b, c is equal to or less than 1, and a + b + c =1.
Further, in the step S1, the molar ratio of the alkali metal M powder to the boron powder is 1-10: 1-6;
and/or the temperature of the vacuum hot extrusion is 1000-1500 ℃, the pressure is 10-500 Mpa, and the heat preservation time is 0.5-6 h.
Further, in the step S2, the temperature of the hot extrusion is 700-1200 ℃, the pressure is 10-500 Mpa, and the heat preservation time is 0.5-48 h;
and/or the heating rate of the hot extrusion is 0.01-10 ℃/min.
Further, in step S2, the NaNi is a Fe b Mn c O 2 One method of preparing the powder is:
a. mixing sodium salt and metal salt, and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a to obtain the NaNi a Fe b Mn c O 2 Powder;
in the step a, the sodium salt comprises at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulfite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide and sodium iodide;
and/or the nickel salt comprises at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide and nickel carbonyl;
and/or the iron salt comprises at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate;
and/or the manganese salt comprises at least one of manganese oxide, potassium permanganate and potassium manganate;
and/or the molar ratio of the sodium salt to the metal salt is 0.05-1.25: 0.01-1.
Further, the NaNi a Fe b Mn c O 2 Another method for preparing the powder is:
c. mixing the sodium salt and the precursor salt, and uniformly stirring;
d. c, sintering the mixture obtained in the step c to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein the sodium salt comprises at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate;
and/or the precursor salt comprises at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese iron hydroxide, nickel manganese hydroxide, and nickel iron manganese hydroxide;
and/or the molar ratio of the sodium salt to the precursor salt is 0.01-1.25: 0.01-1.
Further, in the steps b and d, the sintering temperature is 800-1200 ℃, and the sintering time is 0.5-48 h;
and/or the temperature rise rate of the sintering is 0.01-10 ℃/min.
The invention provides a positive plate, which comprises the sodium-ion battery layered oxide composite material or the sodium-ion battery layered oxide composite material prepared by the method.
The invention provides a sodium-ion battery, which comprises the positive plate.
Compared with the prior art, the invention has the beneficial effects that:
1. in the sodium ion battery layered oxide composite material, the B-alkali metal compound with a 3D frame structure is introduced, so that the sodium ion battery layered oxide composite material has good mechanical and thermal stability, and the phase and the structure of the sodium ion battery layered oxide composite material can endure high temperature of more than 400 ℃ and remain unchanged, so that the high-temperature stability of the O3 phase layered oxide can be greatly optimized, and the high-temperature cycle performance of the battery is improved.
2. In the layered oxide composite material of the sodium-ion battery, the existence of alkali metal generates the function of pre-alkali metallization, and the energy density of the material can be improved, so that the capacity and the first coulombic efficiency of the battery are improved.
Drawings
FIG. 1 is a schematic view of a vacuum hot extrusion apparatus for preparing M x B y A schematic view of a material;
FIG. 2 shows Na as a material in example 1 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Preparation and characterization of (2): in FIG. 2, a is a flow chart for preparing the material; b and c in FIG. 2 are Scanning Electron Micrographs (SEM) of the material; in FIG. 2 d is a Transmission Electron Micrograph (TEM) of the material;
FIG. 3 shows Na as material in example 1 of the present invention 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 X-ray diffraction pattern (XRD).
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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The O3 phase layered oxide has the problems of low energy density, poor high-temperature stability and the like, and practical application of the O3 phase layered oxide is limited. At present, the methods of doping and coating elements are adopted to modify O3 phase layered oxide in the prior art, but the methods can only slightly improve the energy density, but cannot solve the problem of poor high-temperature stability, particularly a material system formed with a hard carbon material in practical application.
In order to solve the above problems of the layered oxide, the present invention provides a method for modifying a layered oxide, which improves the high temperature stability of the layered oxide by introducing an alkali metal-B compound having a 3D framework structure, thereby improving the high temperature cycle performance of the battery.
Specifically, the molecular formula of the layered oxide composite material for the sodium-ion battery provided by the invention is M x B y /NaNi a Fe b Mn c O 2 Wherein: m is an alkali metal element, x is more than or equal to 1, and y is less than or equal to 9;0 ≦ a, b, c ≦ 1, and a + b + c =1.
In the present invention, naNi a Fe b Mn c O 2 Is a layered oxide, including O3 phase layered oxide, P2 phase layered oxide, such as NaMnO 2 、NaFeO 2 、NaNiO 2 、NaFe 1/2 Mn 1/2 O 2 And the like.
M x B y The compound is a compound with a 3D porous framework structure generated by reacting alkali metal powder and boron powder, has good mechanical stability and thermal stability, and can bear high temperature of more than 400 ℃ and maintain unchanged phase and structure. Thus, the present invention employs M x B y Modification of layered oxide with M x B y The electrode has excellent thermal stability and higher electrochemical decomposition potential, so that the structural stability can be maintained when the electrode works at high temperature, and the high-temperature cycle performance of the battery cell is improved; second, M x B y The conductive layer also has high conductivity, and can improve the conductivity of the layered oxide; in addition, M x B y The synergistic effect of the alkali metal M and the 3D skeleton can enable the layered oxide positive electrode material to generate the effect of pre-alkali metallization, so that the energy density and the first coulombic efficiency of the battery can be improved.
In the present invention, the D50 particle size of the sodium ion battery layered oxide composite material may be in the range of 0.01 to 25.5. Mu.m, for example, 0.01 to 0.1. Mu.m, 0.1 to 1 μm, 1 to 5 μm, 5 to 10 μm, 10 to 20 μm, 25.5 μm, or the like.
In the invention, the specific surface area of the sodium-ion battery layered oxide composite material can be in the range of 0.01-47.4 m 2 Per g, it may be, for example, from 0.01 to 0.1 m 2 /g、0.1～1 m 2 /g、1～5 m 2 /g、5～10 m 2 /g、10～20 m 2 /g、20～40 m 2 /g、40～47.4 m 2 And/g, etc.
In the present invention, the sodium ion battery layered oxide composite may have a water content of 0.01% to 1.25%, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.4%, 0.5%, 0.8%, 1.0%, 1.25%, or the like.
The invention also discloses a preparation method of the layered oxide composite material for the sodium-ion battery, which comprises the following steps:
s1, mixing alkali metal M powder and boron powder in vacuum or inert atmosphere, and performing vacuum hot extrusion to obtain M x B y A compound;
s2, mixing M x B y Compound, naNi a Fe b Mn c O 2 And mixing the powder, and performing hot extrusion to obtain the layered oxide composite material of the sodium-ion battery.
In the above step S1, since the alkali metal is easily oxidized in air, the step needs to be performed in vacuum or an inert atmosphere (He, ne, ar, etc.) in order to avoid oxidation of the alkali metal. In a preferred embodiment, this step can be performed in a glove box. The molar ratio of alkali metal M powder (M = Li, na, K) to boron powder may be 1 to 10:1 to 6, and may be, for example, 10. In order to promote sufficient contact reaction of the alkali metal powder and the boron powder, it is preferable to select the alkali metal powder and the boron powder as nanoscale powders.
After the alkali metal M powder and the boron powder are fully and uniformly mixed, the mixture is preferably placed in a vacuum hot extrusion device for vacuum hot extrusion treatment. As shown in FIG. 1, in the vacuum hot pressing apparatus, the alkali metal M powder and the boron powder are pressed to be sufficiently in contact with each other, and under a heating condition, solid-phase sintering occursReacting to form M x B y A compound is provided. Wherein, the pressure applied to the powder by the equipment during sintering can be 10-500 Mpa, such as 10 Mpa, 20 Mpa, 50Mpa, 100 Mpa, 200 Mpa, 300 Mpa, 400 Mpa, 500Mpa, etc. The sintering temperature may be 1000 to 1500 ℃, for example, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, etc. The rate of temperature rise can be 0.01-10 deg.C/min, such as 0.01 deg.C/min, 0.1 deg.C/min, 0.5 deg.C/min, 1 deg.C/min, 2 deg.C/min, 5 deg.C/min, 10 deg.C/min, etc. The holding time can be 0.5-6 h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h and the like. M obtained in this step x B y The compound is easily breakable substance, and is crushed, ground and sieved to obtain powdery substance.
In step S2 of the present invention, M is added x B y Powder, naNi a Fe b Mn c O 2 The powder is stirred and mixed and then is placed in a hot extrusion furnace for heat treatment. In the hot extrusion furnace, the holding time can be 0.5-48 h, such as 0.5h, 1h, 2h, 4h, 6h, 8h, 10h, 12h, 18h, 24h, 30h, 40h, 48h and the like.
In this step, M x B y Powder, naNi a Fe b Mn c O 2 After the powder is mixed and hot pressed and sintered, part of NaNi a Fe b Mn c O 2 Powder into M x B y In the apertures of the frame structure (see b-d in fig. 2).
In the present invention, naNi a Fe b Mn c O 2 The powder can be prepared by two methods, one is a method based on metal salt mixing, and the other is a method based on precursor salt mixing.
The method based on metal salt mixing comprises the following steps:
a. mixing sodium salt and metal salt, and performing ball milling and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a to obtain the NaNi a Fe b Mn c O 2 And (3) powder.
In the step a, the sodium salt includes, but is not limited to, at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulfite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide, and sodium iodide. Nickel salts include, but are not limited to, at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel carbonyl; iron salts include, but are not limited to, at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate, ferrous oxalate; manganese salts include, but are not limited to, at least one of manganese oxide, potassium permanganate, and potassium manganate.
In the step a, the sodium salt and the metal salt are NaNi a Fe b Mn c O 2 (0. Ltoreq. A, b, c. Ltoreq.1, and a + b + c = 1). In some embodiments, the molar ratio of sodium salt to metal salt is 0.05 to 1.25: 0.01 to 1. For example, in the preparation of the compound NaFeO 2 When sodium sulfate is used as sodium salt and ferric chloride is used as metal salt, the molar ratio of the sodium salt to the metal salt is 1.
In the step b, the heating rate of sintering is preferably 0.01 to 10 ℃/min, and may be, for example, 0.01 ℃/min, 0.1 ℃/min, 0.5 ℃/min, 1 ℃/min, 2 ℃/min, 5 ℃/min, 10 ℃/min, or the like; the sintering temperature is preferably 800 to 1200 ℃, and may be, for example, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, or the like; the sintering time is preferably 0.5 to 48 hours, and may be, for example, 0.5 hour, 1 hour, 2 hours, 5 hours, 10 hours, 20 hours, 30 hours, 40 hours, 48 hours, or the like.
The method based on precursor salt mixing comprises the following steps:
c. mixing the sodium salt and the precursor salt, and performing ball milling and stirring uniformly;
d. c, sintering the mixture obtained in the step c to obtain NaNi a Fe b Mn c O 2 And (3) powder.
In the step c, the sodium salt includes, but is not limited to, at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate, and sodium phenolate. The precursor salt includes, but is not limited to, at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese iron hydroxide, nickel manganese hydroxide, and nickel iron manganese hydroxide.
In the step c, the sodium salt and the precursor salt are NaNi a Fe b Mn c O 2 (0. Ltoreq. A, b, c. Ltoreq.1, and a + b + c = 1). In some embodiments, the molar ratio of sodium salt to precursor salt is 0.01 to 1.25: 0.01 to 1. For example, in the preparation of the compound NaFe 1/2 Mn 1/2 O 2 When sodium sulfate is used as a sodium salt and ferromanganese oxide is used as a precursor salt, the molar ratio of the sodium salt to the precursor salt is 1.
In the step d, the heating rate of sintering is preferably 0.01 to 10 ℃/min, and may be, for example, 0.01 ℃/min, 0.1 ℃/min, 0.5 ℃/min, 1 ℃/min, 2 ℃/min, 5 ℃/min, 10 ℃/min, or the like; the sintering temperature is preferably 800 to 1200 ℃, and may be, for example, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, or the like; the sintering time is preferably 0.5 to 48 hours, and may be, for example, 0.5 hour, 1 hour, 2 hours, 5 hours, 10 hours, 20 hours, 30 hours, 40 hours, 48 hours, or the like.
On the basis of the layered oxide composite material, the invention also provides a sodium ion battery which comprises a positive plate, a negative plate, a diaphragm and an electrolyte, wherein the diaphragm is arranged to isolate the positive plate from the negative plate.
In the sodium ion battery, the positive plate can be prepared by adopting a plate preparation process commonly used in the field. The preparation method is schematically as follows: and mixing the layered oxide composite material, the conductive agent and the binder to prepare slurry, coating the slurry on at least one side surface of the positive current collector, and drying and tabletting to obtain the positive plate.
In the preparation method of the positive plate, the type and the content of the conductive agent are not particularly limited and can be selected according to actual requirements. In some embodiments, the conductive agent includes at least one of conductive carbon black, carbon nanotubes, acetylene black, graphene, ketjen black, carbon nanofibers, and the like. It is understood that other conductive agents capable of performing the functions of the present application may be selected according to specific needs without departing from the spirit of the present application and are not limited thereto.
In the preparation method of the positive plate, the type and the content of the binder are not particularly limited and can be selected according to actual requirements. In some embodiments, the binder comprises at least one of polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethylcellulose, polymethacrylic acid, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyamide, polyimide, polyacrylate, styrene butadiene rubber, sodium alginate, chitosan, polyethylene glycol, guar gum, and the like.
The kind of the positive electrode current collector is not particularly limited, and may be selected according to actual requirements, for example, the positive electrode current collector may be an aluminum foil, a nickel foil, or a polymer conductive film, and preferably, the positive electrode current collector is an aluminum foil.
In the sodium ion battery, the type of the separator is not particularly limited, and any separator material conventionally used in batteries may be used, for example, polyethylene, polypropylene, polyvinylidene fluoride, nonwoven fabric, multilayer composite films thereof, and modified separators obtained by modifying the separator with ceramic, PVDF, or the like, but the present invention is not limited thereto.
In the sodium ion battery, the electrolyte can be one or more of an organic liquid electrolyte, an organic solid electrolyte, a solid ceramic electrolyte and a gel electrolyte. Preferably, the electrolyte is an organic liquid electrolyte obtained by dissolving a sodium salt in a non-aqueous organic solvent; wherein the sodium salt may comprise sodium difluorophosphate (NaPO) 2 F 2 ) Sodium hexafluorophosphate (NaPF) 6 ) One or more of sodium bis (fluorosulfonyl) imide (NaFSI), sodium bis (trifluoromethanesulfonyl) imide (NaTFSi), and sodium difluorooxalato (NaDFOB). The non-aqueous organic solvent may include one or more of cyclic carbonate, chain carbonate and carboxylate. Wherein, the cyclic carbonate can be selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), butylene carbonate and gamma-butyrolactone; the chain carbonate can be selected from dimethyl carbonate (DMC), diethyl carbonate (D)EC), methyl ethyl carbonate (EMC), methyl Propyl Carbonate (MPC), methyl Acetate (MA), ethyl Acetate (EA), ethyl Propionate (EP).
In some embodiments, the organic liquid electrolyte may further include a certain amount of additives. The additive may comprise one or more of Vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC), vinyl sulfate (DTD), vinyl sulfite (ES), methylene Methanedisulfonate (MMDS), 1, 3-Propane Sultone (PS), propylene sultone (PES), propylene sulfate (TMS), trimethylsilylphosphate (TMSP), trimethylsilylborate (TMSB), fluoroethylene carbonate (FEC).
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
1. XRD test method
Grinding the prepared powder material, transferring the powder material to a glass slide objective table, transferring the glass slide objective table to an X-ray diffractometer, and carrying out scanning test, wherein the scanning range is 10-80 degrees, and the scanning speed is 5 degrees/min.
2. ICP test method
The molecular formula of the pre-alkali metallization material was determined using ICP detection, wherein ICP-AES is collectively referred to as Inductively Coupled Plasma-Atomic Emission spectroscopy (Inductively Coupled Plasma-Atomic Emission spectroscopy), also referred to as Inductively Coupled Plasma-Emission spectroscopy (ICP-OES). The sample was processed as follows:
(1) Weighing: about 0.1g of sample is accurately weighed into a 50ml polytetrafluoroethylene digestion tube, and the mass of the sample is recorded.
(2) An appropriate amount of inorganic acid (typically 5ml of concentrated nitric acid/1 ml of hydrofluoric acid) is added to each weighed sample digestion tube. Covering the cover, putting the stainless steel reaction kettle into the stainless steel reaction kettle, and placing the stainless steel reaction kettle into an oven to heat at 190 ℃ for about 10 hours, and then stopping heating and cooling.
(3) The cooled solution was transferred to a 25ml plastic volumetric flask and finally fixed to volume with deionized water.
(4) Preparing a standard test solution, wherein the standard solution is a national standard substance, and the curve concentration points are respectively as follows: 0. 0.5, 1.0, 2.0, 5.0mg/L;
(5) And (4) performing instrument test, namely firstly making a standard solution calibration curve through an ICP-OES instrument, inputting the mass and the volume of a sample, then sequentially testing the digested solution, and testing after dilution exceeding the curve range.
(6) And determining the final content of the element to be tested in each sample through a spectrogram to obtain a test result.
3. Assembly and testing of soft-package battery cell
Weighing the positive electrode material, the conductive carbon and the PVDF according to the mass ratio of 90. And then weighing the negative hard carbon material, the conductive carbon and the CMC/SBR according to the mass ratio of 85. The pole piece adopts a winding process, the diaphragm is firstly wound for 5/6 turns, then the anode and the cathode are sequentially wound for 8 turns, and finally the anode is wound to ensure that the cathode piece is completely wrapped in the anode. Welding the pole ear and sticking glue on the prepared winding core, sealing the pole ear with an aluminum plastic film, baking the pole ear in a vacuum oven for 40 to 120 hours, taking out the pole ear, and testing the water content (requiring H) 2 O<200 ppm), and then injecting liquid, sealing, aging, forming and carrying out volume test according to a certain liquid injection coefficient and proportion. Wherein the electrolyte is 1M sodium hexafluorophosphate dissolved in the electrolyte in a volume ratio of EC: DEC = 1+5% in solvent of fec.
The assembled battery is placed on a blue electricity standard testing machine for 8 hours, then the testing process is started, and the battery is charged and discharged at 0.1C multiplying power, and the theoretical specific capacity is 130/370 mAh/g (the capacity is designed according to the pre-calculation). And (3) firstly charging and then discharging by adopting 0.1C current, and finally reading and calculating the corresponding capacity value.
Example 1: preparation of Na based on precursor salt 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2
(1) Adding precursor salts nickel iron manganese hydroxide and sodium carbonate into a reaction vessel according to the molar ratio of 1. Then, the mixture is subjected to solid state sintering treatment, the heating temperature is 1000 ℃, the heating rate is 5.5 ℃/min, the heat preservation time is 12.5 hours, and the NaNi is obtained 0.34 Fe 0.33 Mn 0.33 O 2 A powder;
(2) Mixing nano sodium powder and B powder in a glove box according to a molar ratio of 5; then transferring the mixture to a vacuum extrusion device, and sintering at 1500 deg.C and 250Mpa for 3.5 hr to obtain Na with 3D frame structure 5 B 4 A compound;
(3) Mixing Na 5 B 4 Compound and NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Uniformly stirring and mixing the powder, transferring the powder into a vacuum hot extrusion sintering furnace, heating to 900 ℃ at the heating rate of 10 ℃/min, and carrying out heat preservation sintering for 4 hours under the pressure of 180Mpa to obtain Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 And (3) powder.
Example 2: preparation of Na based on Metal salts 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 2 differs from example 1 in that: in the step (1), the NaNi is prepared by taking sodium carbonate, nickel nitrate, ferrous oxalate and manganese oxide as raw materials, wherein the molar ratio of the sodium carbonate to the nickel nitrate is 0.55 0.34 Fe 0.33 Mn 0.33 O 2 The other steps are the same.
Example 3: preparation K 5 B 4 //NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 3 differs from example 1 in that: the step (2) adopts nano potassium powder.
Example 4: preparation K 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 4 differs from example 2 in that: the step (2) adopts nano potassium powder.
Example 5: preparation of Li 5 B 4 //NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 5 differs from example 1 in that: the step (2) adopts nano lithium powder.
Example 6: preparation of K 3 B 2 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 6 differs from example 1 in that: the step (2) adopts nano potassium powder, and the molar ratio of the nano potassium powder to the B powder is 3.
Example 7: preparation of Na 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 7 differs from example 1 in that: the molar ratio of the nano sodium powder to the B powder in the step (2) is 2.
Example 8: preparation of Na 3 B 2 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 8 differs from example 1 in that: in the step (2), the molar ratio of the nano sodium powder to the B powder is 3.
Example 9: preparation K 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 9 differs from example 1 in that: the step (2) adopts nano potassium powder, and the molar ratio of the nano potassium powder to the B powder is 2.
Example 10: preparation of Li 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 10 differs from example 1 in that: the step (2) adopts nano lithium powder, and the molar ratio of the nano lithium powder to the B powder is 2.
Comparative example 1: preparation of NaNi 0.34 Fe 0.33 Mn 0.33 O 2
The preparation method is the same as the step (1) of the example 1.
The following is directed to example 1Prepared NaNi 0.34 Fe 0.33 Mn 0.33 O 2 And Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 And performing characterization tests.
TABLE 1 NaNi 0.34 Fe 0.33 Mn 0.33 O 2 ICP test results for materials. As can be seen from the results in the table, the molecular formula of the layered oxide material prepared in step (1) of example 1 is NaNi 0.34 Fe 0.33 Mn 0.33 O 2 。
TABLE 1
In FIG. 2, a is Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 A preparation flow chart of the composite material.
In FIG. 2, b and c are Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Scanning Electron Microscopy (SEM) of the composite, from which it can be seen that NaNi 0.34 Fe 0.33 Mn 0.33 O 2 The material was uniformly attached to Na 5 B 4 In the 3D framework of (1).
In FIG. 2 d is Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Transmission Electron Microscopy (TEM) of the composite, from which it can be seen that NaNi 0.34 Fe 0.33 Mn 0.33 O 2 And Na 5 B 4 Are bonded together.
FIG. 3 is Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 The XRD diffraction pattern of the composite material can be seen from the figure, the material is basically consistent with the standard peak of an O3 phase standard card and is consistent with the prior document; in addition, naNi 0.34 Fe 0.33 Mn 0.33 O 2 Is shifted due to the introduction of Na 5 B 4 So that the characteristic peaks appear shifted.
Na prepared as in example 1 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 As the positive electrode active material, the assembled sodium ion soft package battery realizes the initial specific capacity of about 140.5 mA h/g in the voltage range of 2-4V. After the material is cycled for 100 circles at the temperature of 25/45/60/100 ℃, the specific discharge capacity of the material is 133.6/129.2/120.4/107.98mA h/g respectively, and the material has very excellent high-temperature cycle performance.
Na prepared as in example 2 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 As the positive electrode active material, the assembled sodium ion pouch cell achieved an initial specific capacity of about 126.2mA h/g in a voltage range of 2-4V. After the material is cycled for 100 circles at 25/45/60/100 ℃, the specific discharge capacity of the material is 115.8/110.5/100.3/91.4 mA h/g respectively. Is reduced compared with the embodiment 1.
As a comparison, naNi prepared in comparative example 1 0.34 Fe 0.33 Mn 0.33 O 2 As the positive electrode active material, the assembled sodium ion soft package battery realizes the initial specific capacity of about 106.8mA h/g in the voltage range of 2-4V. After the material is cycled for 100 circles at the temperature of 25/45/60/100 ℃, the specific discharge capacity of the material is 95.5/85.3/80.3/71.15mA h/g respectively. This indicates that Na having a 3D framework structure is not introduced 5 B 4 The performance of the battery is remarkably reduced by the compound.
The test results of the other examples are shown in table 2.
TABLE 2
| Molecular formula | Current density 0.1C, discharge The specific capacity (mA h- g) | First library Lung-effect Percentage ratio% | Circulating at 25 ℃ for 100 circles Specific capacity (mA h- g) | Circulating at 45 ℃ for 100 circles Specific capacity (mA h- g) | Circulating at 60 ℃ for 100 circles Specific capacity (mA h- g) | 100 cycles at 100 DEG C Specific capacity (mA h/g) | |
| Fruit of Chinese wolfberry Applying (a) to Example 1 | Na 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 140.5 | 86.1 | 133.6 | 129.2 | 120.4 | 107.98 |
| Fruit of Chinese wolfberry Applying (a) to Example 2 | Na 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 126.2 | 81.6 | 115.8 | 110.5 | 100.3 | 91.4 |
| To pair Ratio of Example 1 | NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 106.8 | 71.4 | 95.5 | 85.3 | 77.3 | 71.15 |
| Fruit of Chinese wolfberry Applying (a) to Example 3 | K 5 B 4 // NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 128.4 | 85.6 | 120.5 | 110.4 | 100.5 | 91.66 |
| Fruit of Chinese wolfberry Applying (a) to Example 4 | K 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 120.65 | 80.8 | 118.66 | 108.3 | 97.8 | 90.32 |
| Fruit of Chinese wolfberry Applying (a) to Example 5 | Li 5 B 4 // NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 121.4 | 81.5 | 119.2 | 109.5 | 99.3 | 91.5 |
| Fruit of Chinese wolfberry Applying for medical instruments Example 6 | K 3 B 2 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 120.9 | 80.99 | 118.9 | 108.9 | 98.0 | 90.5 |
| Fruit of Chinese wolfberry Applying (a) to Example 7 | Na 2 B/ NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 121.5 | 81.3 | 119.4 | 109.6 | 99.2 | 91.3 |
| Fruit of Chinese wolfberry Applying (a) to Example 8 | Na 3 B 2 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 121.1 | 81.0 | 119.1 | 109.2 | 99.0 | 90.8 |
| Fruit of Chinese wolfberry Applying (a) to Example 9 | K 2 B/ NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 119.8 | 79.9 | 118.0 | 105.5 | 96.3 | 89.4 |
| Fruit of Chinese wolfberry Applying for medical instruments Example (b) 10 | Li 2 B/ NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 115.5 | 78.8 | 110.3 | 100.8 | 92.3 | 85.7 |
From the results of table 2 it can be seen that: in comparative example 1, the pure layered oxide NaNi was used 0.34 Fe 0.33 Mn 0.33 O 2 As the anode material, the obtained sodium ion battery has the lowest specific discharge capacity, the lowest initial coulombic efficiency and the lowest specific volume after 100 cycles of circulation at different temperatures.
In example 1, in the layered oxide NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Into which Na having a 3D framework structure is introduced 5 B 4 After the compound, the good mechanical and thermal stability of the compound improves O3 phase layered oxide NaNi 0.34 Fe 0.33 Mn 0.33 O 2 High temperature ofStability and Na 5 B 4 The existence of the alkali metal Na in the compound generates a pre-sodium treatment effect, and the energy density of the material is improved, so that compared with the comparative example 1, the discharge specific capacity, the first coulombic efficiency and the specific capacity after 100 cycles of circulation at different temperatures of the battery in the embodiment 1 are obviously improved.
Also, in examples 2 to 10, M having a 3D frame structure was introduced x B y After the compound is added, the specific discharge capacity and the first coulombic efficiency of the battery are compared with the specific capacity of a pure homogeneous layered oxide NaNi after the battery is cycled for 100 circles at different temperatures 0.34 Fe 0.33 Mn 0.33 O 2 Are all further improved.
In conclusion, the invention introduces M with a 3D framework structure into the layered oxide x B y The compound can greatly improve the cycle performance of the battery, and simultaneously well compensate the initial coulomb efficiency of the loss of the full battery.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The layered oxide composite material for the sodium-ion battery is characterized in that the molecular formula of the layered oxide composite material for the sodium-ion battery is M x B y /NaNi a Fe b Mn c O 2 Wherein: m is an alkali metal element, x is more than or equal to 1, and y is less than or equal to 9;0 ≦ a, b, c ≦ 1, and a + b + c =1.
2. The layered oxide composite material for the sodium-ion battery according to claim 1, wherein the D50 particle size of the layered oxide composite material for the sodium-ion battery is 0.01-25.5 μm;
and/or the specific surface area of the layered oxide composite material of the sodium-ion battery is 0.01-47.4 m 2 /g；
And/or the water content of the sodium-ion battery layered oxide composite material is 0.01-1.25%.
3. The preparation method of the layered oxide composite material of the sodium-ion battery is characterized by comprising the following steps of:
s1, mixing alkali metal M powder and boron powder in vacuum or inert atmosphere, and performing vacuum hot extrusion to obtain M x B y A compound;
s2, mixing M x B y Compound, naNi a Fe b Mn c O 2 After the powder is mixed, carrying out hot extrusion to obtain the layered oxide composite material of the sodium-ion battery;
wherein, in the step S1, x is more than or equal to 1, and y is less than or equal to 9;
in step S2, 0 is equal to or less than a, b, c is equal to or less than 1, and a + b + c =1.
4. The preparation method of the layered oxide composite material for the sodium-ion battery, according to claim 3, wherein in the step S1, the molar ratio of the alkali metal M powder to the boron powder is 1-10: 1-6;
and/or the temperature of the vacuum hot extrusion is 1000-1500 ℃, the pressure is 10-500 Mpa, and the heat preservation time is 0.5-6 h.
5. The preparation method of the layered oxide composite material for the sodium-ion battery according to claim 3, wherein in the step S2, the temperature of the hot extrusion is 700-1200 ℃, the pressure is 10-500 Mpa, and the heat preservation time is 0.5-48 h;
and/or the heating rate of the hot extrusion is 0.01-10 ℃/min.
6. The method for preparing the layered oxide composite material for the sodium-ion battery according to claim 3, wherein in the step S2, the NaNi is added a Fe b Mn c O 2 The preparation method of the powder comprises the following steps:
a. mixing sodium salt and metal salt, and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a to obtain the NaNi a Fe b Mn c O 2 Powder;
in the step a, the sodium salt comprises at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulfite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide and sodium iodide;
and/or the nickel salt comprises at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide and nickel carbonyl;
and/or the iron salt comprises at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate;
and/or the manganese salt comprises at least one of manganese oxide, potassium permanganate and potassium manganate;
and/or the molar ratio of the sodium salt to the metal salt is 0.05-1.25: 0.01-1.
7. The method for preparing the layered oxide composite material for the sodium-ion battery according to claim 3, wherein in the step S2, the NaNi is added a Fe b Mn c O 2 The preparation method of the powder comprises the following steps:
c. mixing the sodium salt and the precursor salt, and uniformly stirring;
d. c, sintering the mixture obtained in the step c to obtain the NaNi a Fe b Mn c O 2 Powder;
wherein the sodium salt comprises at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate;
and/or the precursor salt comprises at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese iron hydroxide, nickel manganese hydroxide and nickel iron manganese hydroxide;
and/or the molar ratio of the sodium salt to the precursor salt is 0.01-1.25: 0.01-1.
8. The method for preparing the layered oxide composite material for the sodium-ion battery according to claim 6 or 7, wherein in the steps b and d: the sintering temperature is 800-1200 ℃, and the sintering time is 0.5-48 h;
and/or the temperature rise rate of the sintering is 0.01-10 ℃/min.
9. A positive electrode sheet comprising the sodium-ion battery layered oxide composite material according to claim 1 or 2 or the sodium-ion battery layered oxide composite material produced by the method according to any one of claims 3 to 8.
10. A sodium ion battery comprising the positive electrode sheet according to claim 9.
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