CN111403729A - Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery - Google Patents
Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery Download PDFInfo
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- CN111403729A CN111403729A CN201911389105.XA CN201911389105A CN111403729A CN 111403729 A CN111403729 A CN 111403729A CN 201911389105 A CN201911389105 A CN 201911389105A CN 111403729 A CN111403729 A CN 111403729A
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- electrode material
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 67
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000011162 core material Substances 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 35
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 229910052718 tin Inorganic materials 0.000 claims abstract description 21
- 239000011258 core-shell material Substances 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 58
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011656 manganese carbonate Substances 0.000 claims description 12
- 235000006748 manganese carbonate Nutrition 0.000 claims description 12
- 229940093474 manganese carbonate Drugs 0.000 claims description 12
- 229940099596 manganese sulfate Drugs 0.000 claims description 12
- 239000011702 manganese sulphate Substances 0.000 claims description 12
- 235000007079 manganese sulphate Nutrition 0.000 claims description 12
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 12
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 12
- 239000012716 precipitator Substances 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 229910014834 Na0.7MnO2 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004436 sodium atom Chemical group 0.000 claims description 2
- 239000011824 nuclear material Substances 0.000 claims 3
- 239000011257 shell material Substances 0.000 abstract description 24
- 239000010405 anode material Substances 0.000 abstract description 16
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 48
- 150000001875 compounds Chemical class 0.000 description 29
- 239000010936 titanium Substances 0.000 description 26
- 239000010949 copper Substances 0.000 description 24
- 239000011135 tin Substances 0.000 description 23
- 239000011777 magnesium Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- -1 transition metal salt Chemical class 0.000 description 8
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 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
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 positive electrode material, a preparation method thereof and a sodium ion battery. The anode material has a core-shell structure, and the core composition is NaxFeyM1‑yO2(ii) a The shell has a composition of NazMnO2；0.6<x≤1，0.5≤y<1，0.44≤z<1; m is one or more of Mn, Ni, Ti, Cu, Sn, Mg, Co, V, Cr and Nd. The preparation method of the cathode material is simple in process, and the prepared cathode material has the advantages of low price, high safety, low requirement on battery manufacturing environment and the like, and can be applied to preparation of sodium-ion batteries. The shell material and the core material of the invention can generate ingenious mutual synergistic effect, thereby improving the charge-discharge specific capacity, the battery cycle performance and the rate performance of the anode material, in particular the cycle stability of the batteryHas outstanding advantages.
Description
Technical Field
The invention relates to a sodium ion battery, in particular to a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery.
Background
The secondary battery system suitable for large-scale energy storage application has the characteristics of wide resources, low price, environmental friendliness, safety and reliability, and simultaneously gives consideration to the requirements of electrochemical performance indexes such as energy density, power density and the like. The existing large-scale secondary battery energy storage technology has various routes, such as a lead-acid battery, a flow battery, a sodium-sulfur battery, a lithium ion battery and the like. However, these batteries have the disadvantages of high cost, limited resources, poor cycle life, poor safety and the like, and cannot meet the requirements of practical application of large-scale energy storage.
In recent years, sodium ion batteries are green, safe, inexpensive, have great advantages as energy storage applications, and have attracted extensive attention in the field of energy storage. However, the factor restricting the development of the sodium ion battery is that the selectable anode and cathode material systems are very limited, the transition metal oxide is one of the current research hotspots, and the transition metal oxide is similar to the commercialized lithium ion battery ternary material, lithium cobaltate and the like, and probably realizes the commercialization of the sodium ion battery firstly. However, the prior transition metal oxide material has the defects of low sodium storage capacity, poor stability, excessive side reaction between the electrode material and the electrolyte and the like, and the factors prevent the transition metal oxide anode material from being further applied on a large scale.
Disclosure of Invention
The invention aims to overcome the defects of low charge and discharge capacity, poor stability and excessive side reaction of an electrode material and an electrolyte of a transition metal oxide material of a sodium-ion battery in the prior art, and provides a positive electrode material of the sodium-ion battery, a preparation method of the positive electrode material and the sodium-ion battery.
At present, if a material containing transition metal elements such as nickel iron and the like is independently used as a positive electrode material, the defects of easy moisture absorption, overhigh surface alkalinity after moisture absorption and the like exist, the defects can cause the decomposition and gas production of electrolyte, and the cycle performance of the battery is attenuated too fast. Sodium manganate is conventionally used alone as a positive electrode material, and has a characteristic of sodium intercalation/deintercalation, but it has a large polarization and a low capacity. The inventor of the application finds that the core-shell structure cathode material is prepared by combining the layered material containing transition metal elements such as nickel iron and the like with sodium manganate, the shell material and the core material generate ingenious mutual synergistic effect, the charge-discharge specific capacity, the battery cycle performance and the rate capability of the cathode material are improved, and particularly the cycle stability of the battery has outstanding advantages.
The invention solves the technical problems through the following technical scheme.
The invention provides a positive electrode material of a sodium ion battery, which has a core-shell structure, wherein the core consists of NaxFeyM1-yO2(ii) a The shell has a composition of NazMnO2；
Wherein x is more than 0.6 and less than or equal to 1, y is more than or equal to 0.5 and less than or equal to 1, and z is more than or equal to 0.44 and less than or equal to 1; m is one or more of Mn, Ni, Ti, Cu, Sn, Mg, Co, V, Cr and Nd.
In the present invention, the Na iszMnO2The mass fraction of the sodium ion battery positive electrode material is preferably more than 1%, and more preferably 1-5%.
In the present invention, x is preferably 0.65 to 0.95, for example, 0.65, 0.8, 0.9 or 0.95.
In the present invention, y is preferably 0.5 to 0.95, more preferably 0.5 to 0.85, for example, 0.5, 0.6 or 0.8.
In the present invention, z is preferably 0.5 to 0.9, for example, 0.5, 0.7, 0.8, 0.9.
In the present invention, M is preferably one or more of Mn, Ni, Ti, Cu, Sn and Mg, more preferably includes Mn and Ni, and further includes one or more of Ti, Cu, Sn and Mg, and even more preferably one or more of "a mixture of Mn, Ni and Ti", "a mixture of Mn, Ni, Ti and Cu", "a mixture of Mn, Ni, Cu and Sn" and "a mixture of Mn, Ni, Sn and Mg", and most preferably "a mixture of Mn, Ni and Ti" or "a mixture of Mn, Ni, Cu and Sn", and even most preferably "a mixture of Mn, Ni and Ti".
In the invention, the preferable composition of the positive electrode material of the sodium-ion battery is that Na is used as a core0.8Fe0.6Mn0.1Ni0.2Ti0.1O2The shell is Na0.5MnO2The core of the positive electrode material is Na0.9Fe0.5Mn0.1Ni0.2Ti0.1Cu0.1O2The shell is Na0.8MnO2The core of the positive electrode material is Na0.95Fe0.5Mn0.2Ni0.1Cu0.1Sn0.1O2The shell is Na0.9MnO2The positive electrode material or core is Na0.67Fe0.5Mn0.1Ni0.2Mg0.1Sn0.1O2The shell is Na0.7MnO2The positive electrode material of (1).
The invention also provides a preparation method of the sodium-ion battery positive electrode material, which comprises the following steps:
1) sintering the mixture of the precursor and the sodium salt to obtain a core material, wherein the core composition is NaxFeyM1-yO2；
The precursor is a solid obtained by mixing and reacting a mixed aqueous solution of ferric salt and M salt, a precipitator and a complexing agent; m is one or more of Mn, Ni, Ti, Cu, Sn, Mg, Co, V, Cr and Nd; the molar ratio of sodium atoms, iron atoms and M atoms is x: y: (1-y), x is more than 0.6 and less than or equal to 1, and y is more than or equal to 0.5 and less than or equal to 1;
2) coating manganese carbonate on the surface of the core material, mixing the obtained solid with sodium salt, and sintering to obtain the cathode material with the core-shell structure;
wherein the core is composed of the NaxFeyM1-yO2(ii) a The shell has a composition of NazMnO2；0.44≤z<1。
The Na iszMnO2The mass fraction of the sodium ion battery positive electrode material is preferably more than 1%, and more preferably 1-5%.
The x is preferably 0.65-0.95, such as 0.65, 0.8, 0.9 or 0.95.
The y is preferably 0.5 to 0.95, more preferably 0.5 to 0.85, such as 0.5, 0.6 or 0.8.
The z is preferably 0.5 to 0.9, for example 0.5, 0.7, 0.8, 0.9.
The M is preferably one or more of Mn, Ni, Ti, Cu, Sn and Mg, more preferably includes Mn and Ni, and further includes one or more of Ti, Cu, Sn and Mg, further preferably one or more of "a mixture of Mn, Ni and Ti", "a mixture of Mn, Ni, Ti and Cu", "a mixture of Mn, Ni, Cu and Sn" and "a mixture of Mn, Ni, Sn and Mg", most preferably "a mixture of Mn, Ni and Ti" or "a mixture of Mn, Ni, Cu and Sn", and further most preferably "a mixture of Mn, Ni and Ti".
The preferable composition of the positive electrode material of the sodium-ion battery is that Na is taken as a core0.8Fe0.6Mn0.1Ni0.2Ti0.1O2The shell is Na0.5MnO2The core of the positive electrode material is Na0.9Fe0.5Mn0.1Ni0.2Ti0.1Cu0.1O2The shell is Na0.8MnO2The core of the positive electrode material is Na0.95Fe0.5Mn0.2Ni0.1Cu0.1Sn0.1O2The shell is Na0.9MnO2The positive electrode material or core is Na0.67Fe0.5Mn0.1Ni0.2Mg0.1Sn0.1O2The shell is Na0.7MnO2The positive electrode material of (1).
In the step 1), the sodium salt is a sodium salt conventionally used in the field of sodium ion battery cathode materials, and preferably comprises one or more of sodium carbonate, sodium nitrate and sodium acetate.
In step 1), the atmosphere for the sintering may be a conventional operation in the art, and an air atmosphere is preferred. The sintering temperature is conventional in the field, and is preferably 700-1000 ℃, preferably 750 ℃, 850 ℃ or 900 ℃. The sintering time is conventional in the art and is preferably from 10 to 25 hours.
In step 1), the product after sintering is preferably cooled. The cooling operation may be conventional in the art, and is preferably natural cooling to room temperature.
In the step 1), the iron salt may be a conventional ferrous salt in the field of sodium ion battery positive electrode materials, preferably including ferrous sulfate and/or ferrous chloride, and further preferably including ferrous sulfate.
In the step 1), the M salt may be a salt containing M atoms, which is conventional in the field of positive electrode materials of sodium-ion batteries, and preferably includes one or more of chloride, sulfate or nitrate, and more preferably is a sulfate.
In the step 1), the concentration of the mixed aqueous solution can be conventional in the field, and is preferably 1-2 mol/L.
In step 1), the water in the mixed aqueous solution is preferably deionized water.
In the step 1), the precipitant is a conventional precipitant in the field of sodium ion battery positive electrode materials, preferably an aqueous solution of sodium hydroxide, and the concentration of the precipitant is conventional in the field, preferably 2-5 mol/L.
In the step 1), the complexing agent is a conventional complexing agent in the field of sodium ion battery positive electrode materials, preferably an aqueous solution of ammonia water, wherein the ammonia water is conventional in the field, and the concentration of the complexing agent is conventional in the field, preferably 2-5 mol/L.
In step 1), the precursor is preferably a solid obtained by adding the mixed aqueous solution, the precipitant and the complexing agent into a reaction kettle in parallel for coprecipitation reaction.
Wherein the temperature of the reaction is conventional in the art, preferably from 40 to 60 ℃. The reaction time is conventional in the art and is preferably from 5 to 10 hours. The pH of the reaction is conventional in the art and is preferably from 9.0 to 11. The stirring speed of the reaction kettle is conventional in the art.
After the coprecipitation reaction, the obtained reaction solution is preferably aged, filtered, washed, and dried to obtain a precursor. The precursor is in a powder state.
The aging enables the reaction to be more complete, and the chemical composition of the precipitate is as close as possible to the charging proportion of the original metal elements. The aging may be carried out by means of aging customary in the art, preferably by leaving to stand. The basic morphology of the precipitate can be kept as much as possible by adopting a standing mode. The standing time can be conventional in the field, and is preferably 10-15 h. After standing for 10-15 h, the surface of the precipitate can form a stable structure, and the basic morphology of the precipitate is prevented from being damaged in the subsequent filtering, washing and drying processes.
The filtration is a routine operation in the art. The washing is a routine operation in the art, preferably with deionized water. The number of washes is conventional in the art, preferably two. The drying is a conventional operation in the field, and preferably drying is carried out for 9-12 hours at 100-120 ℃.
In step 2), the operation and conditions of the coating of manganese carbonate may be conventional in the art, and the core material is generally subjected to a precipitation reaction in a solution containing manganese salt and carbonate.
The manganese salt may be conventional in the art, such as manganese sulfate. The carbonate may be conventional in the art, for example sodium carbonate and/or potassium carbonate. The solvent in the solution may be any solvent that can disperse the core material, and dissolve the manganese salt and the carbonate, as is conventional in the art, and may be, for example, a solvent that disperses the core material with an alcohol and dissolves the manganese salt and the carbonate with water. The concentration of the manganese salt, the concentration of the core material, and the concentration of the carbonate in the solution are conventional in the art.
The operation and conditions of the precipitation reaction can be conventional in the field, and preferably, the precipitation reaction can be carried out on an alcohol solution containing a core material, a manganese sulfate aqueous solution and a sodium carbonate aqueous solution, wherein in the alcohol solution of the core material, the type of a solvent alcohol can be conventional in the field, and the core material can be generally dispersed, such as methanol and/or ethanol, the concentration of the manganese sulfate aqueous solution can be conventional in the field, and is preferably 1-2 mol/L, and the concentration of the sodium carbonate aqueous solution can be conventional in the field, and is preferably 1-2 mol/L.
Among them, after the precipitation reaction, the operation of the post-treatment is preferably performed. The work-up may be carried out as is conventional in the art, and is preferably carried out by filtration, washing and drying. The filtration is a routine operation in the art. The washing is a routine operation in the art, preferably with deionized water. The number of washes is conventional in the art, and is preferably two. The drying is a conventional operation in the field, and preferably drying is carried out for 9-12 hours at 100-150 ℃.
In the step 2), the sodium salt is a sodium salt conventionally used in the field of sodium ion battery cathode materials, and preferably comprises one or more of sodium carbonate, sodium nitrate and sodium acetate.
In step 2), the operations and conditions of the mixing may be conventional in the art.
In step 2), the atmosphere for sintering may be conventional in the art, and an air atmosphere is preferred. The sintering temperature is conventional in the field, and is preferably 700-1000 ℃. The sintering time is conventional in the art and is preferably from 10 to 25 hours.
In step 2), the product after sintering is preferably cooled. The cooling operation may be conventional in the art, and is preferably natural cooling to room temperature.
The invention also provides the positive electrode material of the sodium-ion battery prepared by the preparation method.
The invention also provides a sodium-ion battery which adopts the positive electrode material of the sodium-ion battery.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the positive electrode material of the sodium ion battery prepared by the invention has a core-shell structure, the core is a layered compound, the shell is sodium manganate, and the shell material can effectively prevent the layered compound from contacting with an electrolyte, so that the contact area of the electrode material and the organic electrolyte is obviously reduced, the occurrence of side reactions is reduced, and the gas production speed in the charging and discharging processes of the battery is further reduced. Most importantly, the shell material and the core material have ingenious mutual synergistic effect, the charge-discharge specific capacity, the battery cycle performance and the rate capability of the anode material are improved, and particularly the cycle stability of the battery has outstanding advantages.
2. The preparation method of the anode material provided by the invention is simple in process, and the prepared anode material has the advantages of low price, high safety, low requirement on battery manufacturing environment and the like.
3. The positive electrode material of the sodium-ion battery can be applied to the preparation of the sodium-ion battery. Compared with a lithium ion battery, the sodium ion battery is green, safe and cheap, and has great advantages when being used as an energy storage application.
Drawings
FIG. 1 is an XRD (X-ray diffraction) spectrum of a sodium ion battery cathode material with a core-shell structure prepared in example 1 of the invention.
FIG. 2 is a scanning electron microscope image of the positive electrode material of the sodium-ion battery with a nuclear structure prepared in example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of the core-shell structure sodium ion battery cathode material prepared in example 1 of the present invention
Fig. 4 is a charge-discharge curve diagram of the core-shell structure sodium ion battery cathode material prepared in embodiment 1 under different current densities.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
(1) Preparation of layered Compounds
Sequentially weighing ferrous sulfate, manganese sulfate, nickel sulfate and titanyl sulfate to enable the molar ratio of iron to manganese to nickel to titanium to be 0.6: 0.1: 0.2: 0.1 to prepare soluble transition metal salt, preparing the soluble transition metal salt into a mixed salt solution with the concentration of 2 mol/L by adopting deionized water as a solvent, preparing sodium hydroxide into a precipitator with the concentration of 5 mol/L and preparing ammonia water into a complexing agent with the concentration of 5 mol/L, adding the mixed salt solution, the precipitator and the complexing agent into a reaction kettle in parallel flow, carrying out coprecipitation reaction, aging and standing for 12 hours, filtering, washing with deionized water for 2 times, drying at 100 ℃ for 10 hours to obtain precursor powder, uniformly mixing the precursor powder with sodium carbonate, sintering at 900 ℃ for 15 hours in an air atmosphere, and naturally cooling to obtain a layered compound, wherein the composition of the layered compound is Na0.8Fe0.6Mn0.1Ni0.2Ti0.1O2。
(2) Preparation of core-shell structure sodium ion battery anode material
Dispersing the layered compound into ethanol, adding 1 mol/L manganese sulfate aqueous solution and 1 mol/L sodium carbonate aqueous solution under stirring, filtering after reaction, washing for 2 times with deionized water, drying at 150 ℃ for 12h, uniformly mixing the precursor powder coated with manganese carbonate and sodium carbonate (the molar ratio of manganese carbonate to sodium carbonate is 1: 0.25), sintering at 800 ℃ for 10h in air atmosphere, and naturally cooling to obtain the anode material Na with the core-shell structure0.8Fe0.6Mn0.1Ni0.2Ti0.1O2/Na0.5MnO2. The surface shell layer compound accounts for 1 percent of the mass of the anode material.
Example 2
(1) Preparation of layered Compounds
Sequentially weighing ferrous sulfate, manganese sulfate, nickel sulfate, titanyl sulfate and copper sulfate to enable the molar ratio of iron to manganese to nickel to titanium to copper to be 0.5: 0.1: 0.2: 0.1: 0.1 to prepare soluble transition metal salt, adopting deionized water as a solvent, preparing the soluble transition metal salt into a mixed salt solution with the concentration of 1 mol/L, preparing sodium hydroxide into a precipitator with the concentration of 2 mol/L, preparing ammonia water into a complexing agent with the concentration of 2 mol/L, adding the mixed salt solution, the precipitator and the complexing agent into a reaction kettle in parallel flow, carrying out coprecipitation reaction, aging and standing for 15 hours, filtering, washing with deionized water for 2 times, drying at 120 ℃ for 12 hours to obtain precursor powder, uniformly mixing the precursor powder with sodium carbonate, sintering at 850 ℃ for 20 hours in an air atmosphere, and naturally cooling to obtain a layered compound, wherein the composition of Na0.9Fe0.5Mn0.1Ni0.2Ti0.1Cu0.1O2。
(2) Preparation of core-shell structure sodium ion battery anode material
Dispersing the layered compound into ethanol, adding 2 mol/L manganese sulfate aqueous solution and 2 mol/L sodium carbonate aqueous solution under stirring, filtering after the reaction is finished, and washing for 2 times by deionized waterDrying at 140 ℃ for 9h, uniformly mixing the precursor powder coated with the manganese carbonate and sodium carbonate (the molar ratio of the manganese carbonate to the sodium carbonate is 1: 0.4), sintering at 750 ℃ for 12h in an air atmosphere, and naturally cooling to obtain a positive electrode material Na with a core-shell structure0.9Fe0.5Mn0.1Ni0.2Ti0.1Cu0.1O2/Na0.8MnO2. The surface shell layer compound accounts for 5 percent of the mass fraction of the anode material.
Example 3
(1) Preparation of layered Compounds
Sequentially weighing ferrous nitrate, manganese nitrate, nickel nitrate, copper sulfate and tin tetrachloride to enable the molar ratio of iron to manganese to nickel to copper to tin to be 0.5: 0.2: 0.1: 0.1: 0.1 to prepare soluble transition metal salt, adopting deionized water as a solvent, preparing the soluble transition metal salt into a mixed salt solution with the concentration of 1 mol/L, preparing sodium hydroxide into a precipitator with the concentration of 4 mol/L, preparing ammonia water into a complexing agent with the concentration of 4 mol/L, adding the mixed salt solution, the precipitator and the complexing agent into a reaction kettle in parallel flow, carrying out coprecipitation reaction, aging and standing for 10 hours, filtering, washing for 2 times by using deionized water, drying for 10 hours at 110 ℃ to obtain precursor powder, uniformly mixing the precursor powder with sodium carbonate, sintering for 25 hours at 800 ℃ in an air atmosphere, and naturally cooling to obtain a layered compound, wherein the composition of Na0.95Fe0.5Mn0.2Ni0.1Cu0.1Sn0.1O2。
(2) Preparation of core-shell structure sodium ion battery anode material
Dispersing the layered compound into ethanol, adding 1 mol/L manganese sulfate aqueous solution and 1 mol/L sodium carbonate aqueous solution under stirring, filtering after reaction, washing for 2 times with deionized water, drying at 100 ℃ for 12h, uniformly mixing the precursor powder coated with manganese carbonate and sodium carbonate (the molar ratio of manganese carbonate to sodium carbonate is 1: 0.45), sintering at 850 ℃ for 12h in air atmosphere, and naturally cooling to obtain the anode material Na with the core-shell structure0.95Fe0.5Mn0.2Ni0.1Cu0.1Sn0.1O2/Na0.9MnO2. The surface shell layer compound accounts for 3 percent of the mass fraction of the anode material.
Example 4
(1) Preparation of layered Compounds
Sequentially weighing ferrous nitrate, manganese nitrate, nickel nitrate, magnesium nitrate and stannic chloride to enable the molar ratio of iron, manganese, nickel, magnesium and stannic to be 0.5: 0.1: 0.2: 0.1: 0.1 to prepare soluble transition metal salt, adopting deionized water as a solvent, preparing the soluble transition metal salt into a mixed salt solution with the concentration of 1 mol/L, preparing sodium hydroxide into a precipitator with the concentration of 3 mol/L, preparing ammonia water into a complexing agent with the concentration of 3 mol/L, adding the mixed salt solution, the precipitator and the complexing agent into a reaction kettle in parallel flow at the same time, carrying out coprecipitation reaction, aging and standing for 12 hours, filtering, washing for 2 times by using deionized water, drying for 10 hours at 110 ℃ to obtain precursor powder, uniformly mixing the precursor powder with sodium carbonate, sintering for 20 hours at 700 ℃ in an air atmosphere, naturally cooling to obtain a layered compound, wherein the composition of Na0.67Fe0.5Mn0.1Ni0.2Mg0.1Sn0.1O2。
(2) Preparation of core-shell structure sodium ion battery anode material
Dispersing a layered compound into ethanol, adding a 2 mol/L manganese sulfate aqueous solution and a 2 mol/L sodium carbonate aqueous solution under stirring, filtering after the reaction is finished, washing for 2 times by deionized water, drying for 10h at 140 ℃, uniformly mixing the precursor powder coated by manganese carbonate and sodium carbonate (the molar ratio of manganese carbonate to sodium carbonate is 1: 0.35), sintering for 10h at 800 ℃ in an air atmosphere, and naturally cooling to obtain a positive electrode material Na with a core-shell structure0.67Fe0.5Mn0.1Ni0.2Mg0.1Sn0.1O2/Na0.7MnO2. The surface shell layer compound accounts for 4% of the mass fraction of the positive electrode material.
Comparative example 1
A layered compound having a composition of Na was prepared in accordance with the procedure of step (1) of example 10.8Fe0.6Mn0.1Ni0.2Ti0.1O2。
Comparative example 2
A separate shell material having a composition of Na was prepared in the same manner as in step (2) of example 1, except that the layered compound was not added0.5MnO2。
Comparative example 3
A layered compound having a composition of Na was prepared in accordance with the procedure of step (1) of example 20.9Fe0.5Mn0.1Ni0.2Ti0.1Cu0.1O2。
Comparative example 4
A separate shell material having a composition of Na was prepared in the same manner as in step (2) of example 2, except that the layered compound was not added0.8MnO2。
Comparative example 5
A layered compound having a composition of Na was prepared in accordance with the procedure of step (1) of example 30.95Fe0.5Mn0.2Ni0.1Cu0.1Sn0.1O2。
Comparative example 6
A separate shell material having a composition of Na was prepared in the same manner as in the step (2) of example 3, except that the layered compound was not added0.9MnO2。
Comparative example 7
A layered compound having a composition of Na was prepared in accordance with the procedure of step (1) of example 40.67Fe0.5Mn0.1Ni0.2Mg0.1Sn0.1O2。
Comparative example 8
A separate shell material having a composition of Na was prepared in the same manner as in the step (2) of example 4, except that the layered compound was not added0.7MnO2。
Effect example 1
An XRD (X-ray diffraction) spectrum of the positive electrode material of the sodium-ion battery in example 1 is measured by an X-ray diffractometer (D/max-2200/PC, Rigaku Co., L td.), as shown in figure 1, a sharp peak shape and complete crystallization can be seen from the figure, and thus the core structure is known to be a laminated structure, a scanning electron microscope (Sirion 200, FEI Company) is adopted to measure the laminated compound with the core structure of the sodium-ion battery prepared in example 1 and the positive electrode material with the core-shell structure coated by sodium manganate to obtain a scanning electron microscope figure as shown in figures 2 and 3, as shown in figure 2, the laminated compound with the core structure prepared in example 1 is uniform in particle size distribution, and the crystal morphology of crystal grains is obvious, as shown in figure 3, the positive electrode material with the core-shell structure, the sodium manganate coated on the surface can be seen from the scanning electron microscope, the core crystal of the positive electrode material is obvious, and the sodium manganate coated layer is arranged on the surface layer, so that the positive electrode material with the core.
Effect example 2
The electrode materials for sodium ion batteries prepared in examples 1 to 4 were subjected to the ICP test, and the test results thereof are shown in table 1. As can be seen from Table 1, the ICP test results matched the composition of the sodium ion battery electrode material of the present invention (ICP model: iCAP6000Radial, Seimer Feishell scientific Co.). As can be seen from table 1, the actual elemental compositions of the sodium ion battery electrode materials prepared in examples 1 to 4 conform to the expected chemical formulas.
Table 1 ICP testing of examples 1-4
Effect example 3
(1) Preparation of sodium ion battery
1.8g of the positive electrode material prepared in example 1 was weighed, 0.1g of carbon black and 0.1g of polyvinylidene fluoride dissolved in N, N' -methylpyrrolidone were added, and the mixture was uniformly mixed and coated on an aluminum foil to prepare an electrode sheet. In a glove box under argon atmosphere, a metal sodium sheet is used as a counter electrode, Celgard2700 is used as a diaphragm, and 1M NaClO is used4(ii)/PC: EMC (1: 1) is electrolyte and is assembled into the button battery.
(2) Charge and discharge test
And carrying out charge and discharge tests on the battery within the voltage range of 2.0-4.0V. Fig. 4 is a charging and discharging test curve diagram of the positive electrode material of the sodium-ion battery in example 1 under the current density of 10mA/g or 100mA/g, and it can be seen from the graph that the discharging capacity of the positive electrode material of the sodium-ion battery is 123mAh/g, and in addition, when the current density reaches 100mA/g, the discharging capacity of the positive electrode material of the sodium-ion battery prepared in example 1 is 115mAh/g, which shows good large-current discharging capability.
Corresponding sodium ion batteries were prepared in examples 2 to 4 and comparative examples 1 to 8 according to the step (1) of effect example 3, and corresponding charge and discharge tests were performed according to the step (2), and specific test results are shown in table 2. In the test, the current density of the cycle performance test is 100 mA/g.
As can be seen from table 2, after 100 cycles, the capacity retention rate of the battery in example 1 exceeds 96%, and the capacity retention rate after 1000 cycles can reach 90%.
TABLE 2 Battery Charge/discharge and cycling Performance of examples 1-4
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. The positive electrode material of the sodium-ion battery is characterized by having a core-shell structure, wherein the core consists of NaxFeyM1-yO2(ii) a The shell has a composition of NazMnO2；
Wherein x is more than 0.6 and less than or equal to 1, y is more than or equal to 0.5 and less than or equal to 1, and z is more than or equal to 0.44 and less than or equal to 1; m is one or more of Mn, Ni, Ti, Cu, Sn, Mg, Co, V, Cr and Nd.
2. The positive electrode material for sodium-ion batteries according to claim 1, wherein said Na iszMnO2The mass fraction of the positive electrode material of the sodium-ion battery is more than 1%, preferably 1-5%;
x is 0.65-0.95, such as 0.65, 0.8, 0.9 or 0.95;
y is 0.5 to 0.95, preferably 0.5 to 0.85, such as 0.5, 0.6 or 0.8;
z is 0.5 to 0.9, such as 0.5, 0.7, 0.8 or 0.9.
3. The positive electrode material for sodium-ion batteries according to claim 1, wherein M is one or more of Mn, Ni, Ti, Cu, Sn and Mg, preferably comprises Mn and Ni, and further comprises one or more of Ti, Cu, Sn and Mg, more preferably one or more of "mixture of Mn, Ni and Ti", "mixture of Mn, Ni, Ti and Cu", "mixture of Mn, Ni, Cu and Sn" and "mixture of Mn, Ni, Sn and Mg", most preferably "mixture of Mn, Ni and Ti" or "mixture of Mn, Ni, Cu and Sn", and still most preferably "mixture of Mn, Ni and Ti".
4. The positive electrode material for sodium-ion batteries according to claim 1, wherein the composition of the positive electrode material for sodium-ion batteries is such that the core is Na0.8Fe0.6Mn0.1Ni0.2Ti0.1O2The shell is Na0.5MnO2The positive electrode material of (1);
the nucleus is Na0.9Fe0.5Mn0.1Ni0.2Ti0.1Cu0.1O2The shell is Na0.8MnO2The positive electrode material of (1);
the nucleus is Na0.95Fe0.5Mn0.2Ni0.1Cu0.1Sn0.1O2The shell is Na0.9MnO2The positive electrode material of (1);
or, the core is Na0.67Fe0.5Mn0.1Ni0.2Mg0.1Sn0.1O2The shell is Na0.7MnO2The positive electrode material of (1).
5. The preparation method of the positive electrode material of the sodium-ion battery is characterized by comprising the following steps of:
1) sintering the mixture of the precursor and the sodium salt to obtain a core material, wherein the core composition is NaxFeyM1-yO2；
The precursor is a solid obtained by mixing and reacting a mixed aqueous solution of ferric salt and M salt, a precipitator and a complexing agent; m is one or more of Mn, Ni, Ti, Cu, Sn, Mg, Co, V, Cr and Nd; the molar ratio of sodium atoms, iron atoms and M atoms is x: y: (1-y), x is more than 0.6 and less than or equal to 1, and y is more than or equal to 0.5 and less than or equal to 1;
2) coating manganese carbonate on the surface of the core material, mixing the obtained solid with sodium salt, and sintering to obtain the cathode material with the core-shell structure;
wherein the core is composed of the NaxFeyM1-yO2(ii) a The shell has a composition of NazMnO2；0.44≤z<1。
6. The method for producing a positive electrode material for a sodium-ion battery according to claim 5, wherein the Na iszMnO2The amount, said x, said y or said z are as defined in claim 1;
the specific composition of the M or the positive electrode material of the sodium-ion battery is as defined in claim 3 or 4;
and/or, in step 1), the sodium salt comprises one or more of sodium carbonate, sodium nitrate and sodium acetate;
and/or, in the step 1), the sintering atmosphere is air atmosphere;
and/or in the step 1), the sintering temperature is 700-1000 ℃, preferably 750 ℃, 850 ℃ or 900 ℃;
and/or, in the step 1), the sintering time is 10-25 hours;
and/or, in the step 1), cooling the product enough sintered; the cooling operation is preferably natural cooling to room temperature;
and/or, in step 1), the iron salt comprises ferrous sulfate and/or ferrous chloride, preferably ferrous sulfate;
and/or, in the step 1), the M salt comprises one or more of chloride, sulfate or nitrate, and is selected as sulfate;
and/or in the step 1), the concentration of the mixed aqueous solution is 1-2 mol/L;
and/or, in the step 1), the water in the mixed aqueous solution is deionized water;
and/or, in the step 1), the precipitant is an aqueous solution of sodium hydroxide;
and/or in the step 1), the concentration of the precipitant is 2-5 mol/L;
and/or, in the step 1), the complexing agent is an aqueous solution of ammonia water;
and/or in the step 1), the concentration of the complexing agent is 2-5 mol/L.
7. The method for preparing the positive electrode material for the sodium-ion battery according to claim 5, wherein in the step 1), the precursor is a solid obtained by co-currently adding the mixed aqueous solution, the precipitant and the complexing agent into a reaction kettle for a co-precipitation reaction;
the temperature of the reaction is preferably 40-60 ℃; the reaction time is preferably 5 to 10 hours; the pH value of the reaction is preferably 9.0-11;
after the coprecipitation reaction, preferably, the obtained reaction solution is aged, filtered, washed and dried to obtain a precursor; the aging is preferably a standing; the standing time is preferably 10-15 h; preferably, deionized water is adopted for washing; the drying condition is preferably 100-120 ℃ for drying for 9-12 hours.
8. The method for preparing the positive electrode material of the sodium-ion battery according to claim 5, wherein in the step 2), the coating of the manganese carbonate is performed according to the following steps: carrying out precipitation reaction on the nuclear material in a solution containing manganese salt and carbonate;
the manganese salt is preferably manganese sulfate; the carbonate is preferably sodium carbonate and/or potassium carbonate;
the precipitation reaction is preferably carried out according to the following steps of carrying out precipitation reaction on an alcohol solution containing a nuclear material, a manganese sulfate aqueous solution and a sodium carbonate aqueous solution, wherein the type of the alcohol is preferably methanol and/or ethanol in the alcohol solution of the nuclear material, the concentration of the manganese sulfate aqueous solution is preferably 1-2 mol/L, and the concentration of the sodium carbonate aqueous solution is 1-2 mol/L;
after the precipitation reaction, the operation of post-treatment is preferably carried out; the post-treatment is preferably filtration, washing and drying;
and/or, in the step 2), the sodium salt comprises one or more of sodium carbonate, sodium nitrate and sodium acetate;
and/or, in step 2), the sintering atmosphere is air atmosphere;
and/or in the step 2), the sintering temperature is 700-1000 ℃;
and/or, in the step 2), the sintering time is 10-25 hours;
and/or, in the step 2), cooling the product which is sintered enough; the cooling operation is preferably natural cooling to room temperature.
9. The positive electrode material of the sodium-ion battery prepared by the preparation method of any one of claims 5 to 8.
10. A sodium ion battery using the positive electrode material for a sodium ion battery according to any one of claims 1 to 4 or 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114751466A (en) * | 2022-04-24 | 2022-07-15 | 南通金通储能动力新材料有限公司 | Sodium ion battery positive electrode material precursor and preparation method thereof |
| CN114843498A (en) * | 2022-03-30 | 2022-08-02 | 北京当升材料科技股份有限公司 | Sodium-containing oxide positive electrode material, preparation method and application thereof, positive electrode plate and application thereof |
| CN114920306A (en) * | 2022-06-29 | 2022-08-19 | 荆门市格林美新材料有限公司 | Positive electrode material precursor, positive electrode material, preparation method of positive electrode material and sodium ion battery |
| CN115057482A (en) * | 2022-05-18 | 2022-09-16 | 中南大学 | Positive electrode material and precursor of sodium-ion battery and preparation method |
| CN115125069A (en) * | 2022-08-12 | 2022-09-30 | 芜湖天弋能源科技有限公司 | Acid washing detergent for positive electrode material of sodium-ion battery and application thereof |
| CN115377394A (en) * | 2022-09-27 | 2022-11-22 | 上海领钫新能源科技有限公司 | Positive active material for sodium ion battery and preparation method and application thereof |
| CN115557546A (en) * | 2022-12-06 | 2023-01-03 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113629233A (en) * | 2021-08-09 | 2021-11-09 | 清华大学深圳国际研究生院 | P2-O3 composite phase lithium-rich manganese-based lithium ion battery positive electrode material and preparation method and application thereof |
| CN114843498B (en) * | 2022-03-30 | 2023-06-02 | 北京当升材料科技股份有限公司 | Sodium oxide-containing positive electrode material, preparation method and application thereof, positive electrode plate and application thereof |
| CN114843498A (en) * | 2022-03-30 | 2022-08-02 | 北京当升材料科技股份有限公司 | Sodium-containing oxide positive electrode material, preparation method and application thereof, positive electrode plate and application thereof |
| US11984591B1 (en) | 2022-03-30 | 2024-05-14 | Beijing Easpring Material Technology Co., Ltd. | Sodium-containing oxide positive electrode material and preparation method therefor and use thereof, and positive electrode plate and use thereof |
| CN114751466A (en) * | 2022-04-24 | 2022-07-15 | 南通金通储能动力新材料有限公司 | Sodium ion battery positive electrode material precursor and preparation method thereof |
| CN115057482A (en) * | 2022-05-18 | 2022-09-16 | 中南大学 | Positive electrode material and precursor of sodium-ion battery and preparation method |
| CN115057482B (en) * | 2022-05-18 | 2023-07-14 | 中南大学 | Sodium ion battery positive electrode material, precursor and preparation method |
| CN114920306A (en) * | 2022-06-29 | 2022-08-19 | 荆门市格林美新材料有限公司 | Positive electrode material precursor, positive electrode material, preparation method of positive electrode material and sodium ion battery |
| CN114920306B (en) * | 2022-06-29 | 2024-03-26 | 荆门市格林美新材料有限公司 | Positive electrode material precursor, positive electrode material, preparation method of positive electrode material precursor and sodium ion battery |
| CN115125069B (en) * | 2022-08-12 | 2023-11-14 | 芜湖天弋能源科技有限公司 | Acid washing detergent for positive electrode material of sodium ion battery and application thereof |
| CN115125069A (en) * | 2022-08-12 | 2022-09-30 | 芜湖天弋能源科技有限公司 | Acid washing detergent for positive electrode material of sodium-ion battery and application thereof |
| CN115377394A (en) * | 2022-09-27 | 2022-11-22 | 上海领钫新能源科技有限公司 | Positive active material for sodium ion battery and preparation method and application thereof |
| CN115557546B (en) * | 2022-12-06 | 2023-03-21 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN115557546A (en) * | 2022-12-06 | 2023-01-03 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
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