CN117317189A - Positive electrode material of sodium ion battery and preparation method and application thereof - Google Patents
Positive electrode material of sodium ion battery and preparation method and application thereof Download PDFInfo
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- CN117317189A CN117317189A CN202311433474.0A CN202311433474A CN117317189A CN 117317189 A CN117317189 A CN 117317189A CN 202311433474 A CN202311433474 A CN 202311433474A CN 117317189 A CN117317189 A CN 117317189A
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- transition metal
- positive electrode
- electrode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 75
- 229910001415 sodium ion Inorganic materials 0.000 title abstract description 37
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 18
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 42
- 239000000661 sodium alginate Substances 0.000 claims abstract description 42
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 42
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 8
- -1 transition metal salt Chemical class 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 12
- 229940072056 alginate Drugs 0.000 abstract description 7
- 235000010443 alginic acid Nutrition 0.000 abstract description 7
- 229920000615 alginic acid Polymers 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 32
- 238000001035 drying Methods 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000001509 sodium citrate Substances 0.000 description 15
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000000227 grinding Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000017 hydrogel Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 229940099596 manganese sulfate Drugs 0.000 description 8
- 239000011702 manganese sulphate Substances 0.000 description 8
- 235000007079 manganese sulphate Nutrition 0.000 description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 150000002505 iron Chemical class 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 150000002696 manganese Chemical class 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 150000002815 nickel Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910021260 NaFe Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 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
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery materials, and particularly relates to a positive electrode material of a sodium ion battery, and a preparation method and application thereof. A positive electrode material of sodium ion battery comprises layered transition metal oxide with structural formula of Na x MO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.48 and less than or equal to 1; m is a transition metal element. The invention forms the hydrogel-like substance with a net egg-shaped structure by complexing sodium alginate and transition metal ions, and utilizes carboxyl and hydroxyl in the sodium alginate to lead the coordinated alginate radicals to exist between the transition metal ions, thereby being capable of well dispersing the transition metal ions and the sodium ions to obtain the structural formula Na x MO 2 The layered oxide positive electrode material of the sodium ion battery, wherein x is more than or equal to 0.48 and less than or equal to 1, has good structural stability, and cycle stability and doubling performanceRate performance.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a positive electrode material of a sodium ion battery, and a preparation method and application thereof.
Background
The layered oxide of the positive electrode material of the sodium ion battery has a crystal structure similar to that of a ternary positive electrode material, and has good energy density and cycle life, and metal elements in the layered oxide mainly comprise copper, manganese, iron and other elements, so that the metal is sufficiently supplied and relatively low in price. However, sodium transition metal oxide material Na x MO 2 Is highly hygroscopic and absorbs moisture in the air even when exposed to the air for a very short period of time, thereby affecting electrochemical performance.
The existing methods for preparing the layered oxide material include a sol-gel method, a coprecipitation method, a solid phase method and the like, and in commercial application, the coprecipitation method is mainly adopted, and other methods are not suitable for mass preparation due to the problems of cost and preparation technology. However, the layered oxide prepared by the coprecipitation method has larger particles, and requires accurate pH conditions, and has very strict requirements on the precipitant. And most of granular layered oxide materials synthesized by the traditional method are polycrystalline materials, and the conditions of single-crystal layered oxide are very harsh. At the same time, micron-sized "secondary" particles are typically composed of a number of "primary" nanoparticles that allow electrolyte to penetrate into the interior through the interstices between the grains, while the random crystallographic orientation of the primary particles can result in significant stresses during cycling, thereby creating cracks. In addition, the layered oxide prepared by the traditional method is mainly divided into O3 type and P2 type, but the two materials have the defects of poor cycle stability and multiple phase changes in the charge and discharge process, and the multiple phase changes easily cause the collapse of the positive electrode material in the charge and discharge process, so that the battery performance is in an unstable state, and the commercial application of the positive electrode material is affected.
Therefore, it is desirable to provide a positive electrode material having good structural stability, cycle stability and rate capability.
Disclosure of Invention
The present invention is directed to solving one or more of the problems of the prior art and providing at least one of a beneficial choice or creation of conditions. The invention provides a positive electrode material of a sodium ion battery, which has good structural stability, circulation stability and rate capability.
The invention is characterized in that: the invention forms the hydrogel-like substance with a net egg-shaped structure by complexing sodium alginate and transition metal ions, and utilizes carboxyl and hydroxyl in the sodium alginate to lead the coordinated alginate radicals to exist between the transition metal ions, thereby being capable of well dispersing the transition metal ions and the sodium ions to obtain the structural formula Na x MO 2 The sodium ion battery layered oxide anode material with x being more than or equal to 0.48 and less than or equal to 1 has good structural stability, circulation stability and rate capability.
Accordingly, a first aspect of the present invention provides a positive electrode material for a sodium ion battery.
Specifically, the positive electrode material of the sodium ion battery comprises a layered transition metal oxide, wherein the structural formula of the layered transition metal oxide is Na x MO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.48 and less than or equal to 1.
Preferably, when 0.48.ltoreq.x <0.75, the layered transition metal oxide is a P2 type layered oxide; when x is more than or equal to 0.75 and less than or equal to 0.89, the layered transition metal oxide is a P2/O3 composite layered oxide; when x is less than or equal to 0.89 and less than or equal to 1, the layered transition metal oxide is O3 type layered oxide.
Preferably, the M comprises at least one of Ni, mn, co, fe, cu, ti, nb.
Preferably, the layered transition metal oxide has the structural formula Na x Fe y Ni z Mn 1-y-z O 2 ，0.48≤x≤1；0≤y≤1，0≤z≤1。
Preferably, the layered transition metal oxide is of single crystal structure.
Specifically, the monocrystal structure can improve the problems of structural stability, cycle stability, multiplying power performance and the like of the battery, reduce the cost of the layered monocrystal material and accelerate the commercial application of the monocrystal layered oxide anode material of the sodium ion battery.
Preferably, the layered transition metal oxide is a hexagonal block-shaped particle.
Preferably, the thickness of the hexagonal block-shaped particles is 90-550nm; the size of the hexagonal block-shaped particles is 450nm-2.2 μm.
Further preferably, the thickness of the hexagonal block-shaped particles is 100-500nm; the size of the hexagonal block-shaped particles is 500nm-2 μm.
Specifically, the hexagonal block-shaped particles are uniformly distributed.
The second aspect of the invention provides a preparation method of the positive electrode material of the sodium ion battery.
Specifically, the preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
and mixing transition metal salt and sodium alginate, reacting, and calcining to obtain the positive electrode material of the sodium ion battery.
Preferably, the molar ratio of the transition metal salt to the sodium alginate is 1:0.35-2.2; further preferably, the molar ratio of the transition metal salt to the sodium alginate is 1:0.4-2.0.
Preferably, the preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
(1) Mixing transition metal salt solution and sodium alginate solution, and reacting to obtain a precursor;
(2) Calcining the precursor obtained in the step (1) to obtain the positive electrode material of the sodium ion battery.
Preferably, the concentration of transition metal ions in the transition metal salt solution is 0.6-1.5mol/L; further preferably, the concentration of the transition metal ion is 1.0 to 1.4mol/L; still more preferably, the concentration of the transition metal ion is 1.2mol/L.
Preferably, the transition metal salt solution is an aqueous solution of a transition metal salt.
Preferably, the transition metal salt comprises an iron salt, a manganese salt, a nickel salt.
Further preferably, the iron salt is selected from at least one of ferric nitrate, ferric oxalate, ferric chloride, ferric carbonate, ferric sulfate, and ferric acetate; the manganese salt is selected from at least one of manganese sulfate, manganese nitrate, manganese oxalate, manganese chloride, manganese carbonate and manganese acetate, and the nickel salt is selected from at least one of nickel sulfate, nickel acetate, nickel nitrate, nickel oxalate, nickel chloride and nickel carbonate.
Still more preferably, the iron salt, manganese salt, and nickel salt are iron nitrate, manganese sulfate, and nickel sulfate, respectively.
Preferably, the molar ratio of the iron salt, the manganese salt and the nickel salt is 0.8-1.2:0.8-1.2:1, a step of; further preferably, the molar ratio of the iron salt, the manganese salt and the nickel salt is 0.9-1.1:0.9-1.1:1, a step of; still more preferably, the molar ratio of the iron salt, manganese salt, nickel salt is 1:1:1.
preferably, in the sodium alginate solution, the concentration of sodium alginate is 0.6-1.5mol/L; further preferably, the concentration of sodium alginate is 1.0-1.4mol/L; still more preferably, the concentration of sodium alginate is 1.2mol/L.
Preferably, the sodium alginate solution is an aqueous solution of sodium alginate; further preferably, the aqueous solution of sodium alginate is a sodium alginate hydrogel solution.
Specifically, sodium alginate is dissolved in water and stirred to obtain sodium alginate hydrogel solution.
Preferably, the mixing of the transition metal salt solution and the sodium alginate solution is specifically that the transition metal salt solution is added into the sodium alginate solution for mixing.
Preferably, stirring is performed after the mixing; the stirring speed is 100-500rpm; further preferably, the rotational speed of the stirring is 400rpm.
Preferably, the reaction time is 0.5 to 24 hours; further preferably, the reaction time is 2 to 10 hours.
Preferably, the temperature of the reaction is room temperature.
Preferably, the special egg-shaped gel mixed solution is obtained after the reaction.
Preferably, the special egg-shaped gel mixture is dried and ground for the first time to prepare the precursor.
Preferably, the drying is performed in a vacuum drying oven.
Preferably, the drying temperature is 50-180 ℃, and the drying time is 12-18h.
Further preferably, the drying temperature is 50-120 ℃, and the drying time is 14-16h.
Preferably, the drying is followed by natural cooling and then a first grinding.
Preferably, in the step (2), the calcination temperature is 650-1050 ℃, and the calcination time is 4-24 hours.
Further preferably, the calcination temperature is 750-950 ℃ and the calcination time is 8-12h.
Preferably, the temperature rising rate of the calcination is 2-10 ℃/min; further preferably, the temperature rise rate of the calcination is 3 to 6 ℃/min.
Preferably, the calcination further comprises a second grinding, washing and drying process.
Preferably, washing is performed with distilled water.
Preferably, the drying is performed in a vacuum drying oven.
A third aspect of the invention provides a battery.
Specifically, the battery comprises the positive electrode material of the sodium ion battery according to the first aspect of the invention.
Preferably, the battery is a sodium ion battery.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The positive electrode material comprises layered transition metal oxide, wherein the layered transition metal oxide is hexagonal block-shaped particles, and the structural formula of the layered transition metal oxide is Na x MO 2 X is more than or equal to 0.48 and less than or equal to 1, and according to the difference of the value ranges of x, three different types of positive electrode materials of O3 type, P2 type and O3/P2 composite type can be obtained, and the positive electrode material has good structural stability, circulation stability and multiplying power performance.
(2) According to the invention, the sodium alginate and the transition metal ions are complexed to form the hydrogel-like substance with a net egg-shaped structure, and the carboxyl and hydroxyl groups in the sodium alginate are utilized to enable coordinated alginate radicals to exist between the transition metal ions, so that the transition metal ions and the sodium ions can be well dispersed, and the single crystal sodium ion battery layered oxide positive electrode material with uniform particle distribution is obtained.
(3) The preparation method has simple preparation process and mild conditions, is beneficial to large-scale production application and commercialization, and has good economic benefit.
Drawings
FIG. 1 is a schematic diagram of a special egg-shaped structure according to embodiment 1 of the present invention;
FIG. 2 is an XRD pattern of the positive electrode material of example 1 of the present invention;
FIG. 3 is an XRD pattern of the positive electrode material of example 2 of the present invention;
FIG. 4 is an XRD pattern of the positive electrode material of example 3 of the present invention;
FIG. 5 is an SEM image of the positive electrode materials of examples 1-3 and comparative examples 1-3 of the present invention;
FIG. 6 is a HRTEM chart of the positive electrode material of example 3 of the present invention;
fig. 7 is a graph showing cycle performance of CR2032 type coin cells prepared in application example 1 and comparative application example 1 according to the invention;
fig. 8 is a graph showing the cycle performance of CR2032 type coin cells prepared according to application example 2 of the invention and comparative application example 2;
fig. 9 is a graph showing the cycle performance of CR2032 type coin cells prepared according to application example 3 of the invention and comparative application example 3;
fig. 10 is a graph showing the rate performance of CR2032 type coin cells prepared in application example 1 and comparative application example 1 according to the invention;
fig. 11 is a graph showing the rate performance of CR2032 type coin cells prepared according to application example 2 of the invention and comparative application example 2;
fig. 12 is a graph showing the rate performance of CR2032 type coin cells prepared in application example 3 of the invention and comparative application example 3.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1
The preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
(1) According to the mole ratio of 1:1:1, preparing ferric nitrate, manganese sulfate and nickel sulfate into a metal salt solution with the total metal ion concentration of 1mol/L by using distilled water;
(2) The molar ratio of sodium alginate to transition metal ions is 0.67:1, weighing sodium alginate, preparing a sodium alginate aqueous solution with the concentration of 1.0mol/L by adopting water, and stirring to obtain a sodium alginate hydrogel solution;
(3) Dripping the metal salt solution obtained in the step (1) into the sodium alginate hydrogel solution obtained in the step (2) at a flow rate of 1mL/min, keeping the stirring rotation speed at 200rpm, reacting for 4 hours at room temperature to obtain gel mixed solution with a special net egg-shaped structure, drying in an oven, drying at 50 ℃ for 30 hours, naturally cooling, and mechanically grinding to obtain positive electrode material precursor powder;
(4) Calcining the positive electrode material precursor powder obtained in the step (3) in a muffle furnace, heating to 900 ℃ at a heating rate of 2 ℃/min under an air atmosphere, preserving heat for 15h, naturally cooling, grinding, washing with distilled water, and drying in a vacuum drying oven to obtain a compound formula Na 0.67 Fe 0.33 Ni 0.33 Mn 0.33 O 2 P2-type layered oxide sodium ion battery positive electrode material.
The schematic structural diagram of the special net egg-shaped structure obtained in the step (2) is shown in fig. 1, and TM represents a transition metal element. As can be seen from fig. 1, the alginate in the sodium alginate has a plurality of carboxyl groups and hydroxyl groups, and can form hydrogel with a plurality of transition metal ions to form a net egg-shaped structure, and more important sodium ions can be uniformly distributed around the alginate due to the advantage of well dispersing single transition metal ions between the special net egg-shaped structure and the alginate.
Example 2
The preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
(1) According to the mole ratio of 1:1:1, preparing ferric nitrate, manganese sulfate and nickel sulfate into a metal salt solution with the total metal ion concentration of 1mol/L by using distilled water;
(2) The molar ratio of sodium alginate to transition metal ions is 0.89:1, weighing sodium alginate, preparing a sodium alginate aqueous solution with the concentration of 1.0mol/L by adopting water, and stirring to obtain a sodium alginate hydrogel solution;
(3) Dripping the metal salt solution obtained in the step (1) into the sodium alginate hydrogel solution obtained in the step (2) at a flow rate of 1mL/min, keeping the stirring rotation speed at 200rpm, reacting for 4 hours at room temperature to obtain a special net egg-shaped gel mixed solution, drying in an oven, drying at 80 ℃ for 18 hours, naturally cooling, and mechanically grinding to obtain a positive electrode material precursor powder;
(4) Calcining the positive electrode material precursor powder obtained in the step (3) in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under an air atmosphere, preserving heat for 4 hours, heating to 950 ℃ and preserving heat for 15 hours, naturally cooling, grinding, washing with distilled water, and drying in a vacuum drying oven to obtain a compound formula Na 0.89 Fe 0.33 Ni 0.33 Mn 0.33 O 2 P2/O3 composite layered oxide sodium ion battery anode material.
Example 3
The preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
(1) According to the mole ratio of 1:1:1, preparing ferric nitrate, manganese sulfate and nickel sulfate into a metal salt solution with the total metal ion concentration of 1mol/L by using distilled water;
(2) The molar ratio of the sodium alginate to the transition metal ions is 1.3:1, weighing sodium alginate, preparing a sodium alginate aqueous solution with the concentration of 1.0mol/L by adopting water, and stirring to obtain a sodium alginate hydrogel solution;
(3) Dripping the metal salt solution obtained in the step (1) into the sodium alginate hydrogel solution obtained in the step (2) at a flow rate of 1mL/min, keeping the stirring rotation speed at 300rpm, reacting for 6 hours at room temperature to obtain a special net egg-shaped gel mixed solution, drying in an oven, drying at 80 ℃ for 18 hours, naturally cooling, and mechanically grinding to obtain a positive electrode material precursor powder;
(4) Calcining the positive electrode material precursor powder obtained in the step (3) in a muffle furnace, heating to 950 ℃ at a heating rate of 2 ℃/min under an air atmosphere, preserving heat for 15h, naturally cooling, grinding, washing with distilled water, and drying in a vacuum drying oven to obtain NaFe with a chemical formula of 0.33 Ni 0.33 Mn 0.33 O 2 An O3 type layered oxide sodium ion battery positive electrode material.
Comparative example 1
The preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
(1) According to the mole ratio of 1:1:1, preparing ferric nitrate, manganese sulfate and nickel sulfate into a metal salt solution with the total metal ion concentration of 1mol/L by using distilled water;
(2) The molar ratio of sodium citrate to transition metal ions is 0.67:1, weighing sodium citrate, preparing a sodium citrate aqueous solution with 1.0mol/L by adopting water, and stirring to obtain a sodium citrate solution;
(3) Dripping the metal salt solution obtained in the step (1) into the sodium citrate solution obtained in the step (2) at a flow rate of 1mL/min, keeping the stirring rotation speed at 300rpm, reacting for 6 hours at room temperature to obtain a mixed solution, drying in an oven, drying at 80 ℃ for 18 hours, naturally cooling, and mechanically grinding to obtain a positive electrode material precursor powder;
(4) Calcining the positive electrode material precursor powder obtained in the step (3) in a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under an air atmosphere, preserving heat for 15h, naturally cooling, grinding, washing with distilled water, and drying in a vacuum drying oven to obtain a compound formula Na 0.89 Fe 0.33 Ni 0.33 Mn 0.33 O 2 P2 type layered oxide sodium ion battery of (2)And a positive electrode material.
Comparative example 2
The preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
(1) According to the mole ratio of 1:1:1, preparing ferric nitrate, manganese sulfate and nickel sulfate into a metal salt solution with the total metal ion concentration of 1mol/L by using distilled water;
(2) The molar ratio of sodium citrate to transition metal ions is 0.89:1, weighing sodium citrate, preparing a sodium citrate aqueous solution with 1.0mol/L by adopting water, and stirring to obtain a sodium citrate solution;
(3) Dripping the metal salt solution obtained in the step (1) into the sodium citrate solution obtained in the step (2) at a flow rate of 1mL/min, keeping the stirring rotation speed at 200rpm, reacting for 4 hours at room temperature to obtain a mixed solution, drying in an oven, drying at 80 ℃ for 18 hours, naturally cooling, and mechanically grinding to obtain a positive electrode material precursor powder;
(4) Calcining the positive electrode material precursor powder obtained in the step (3) in a muffle furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under an air atmosphere, preserving heat for 4 hours, heating to 950 ℃ and preserving heat for 15 hours, naturally cooling, grinding, washing with distilled water, and drying in a vacuum drying oven to obtain a compound formula Na 0.89 Fe 0.33 Ni 0.33 Mn 0.33 O 2 P2/O3 composite layered oxide sodium ion battery anode material.
Comparative example 3
The preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
(1) According to the mole ratio of 1:1:1, preparing ferric nitrate, manganese sulfate and nickel sulfate into a metal salt solution with the total metal ion concentration of 1mol/L by using distilled water;
(2) The molar ratio of sodium citrate to transition metal ions is 1.3:1, weighing sodium citrate, preparing a sodium citrate aqueous solution with 1.0mol/L by adopting water, and stirring to obtain a sodium citrate solution;
(3) Dripping the metal salt solution obtained in the step (1) into the sodium citrate solution obtained in the step (2) at a flow rate of 1mL/min, keeping the stirring rotation speed at 200rpm, reacting for 4 hours at room temperature to obtain a mixed solution, drying in an oven, drying at 50 ℃ for 18 hours, naturally cooling, and mechanically grinding to obtain a positive electrode material precursor powder;
(4) Calcining the positive electrode material precursor powder obtained in the step (3) in a muffle furnace, heating to 950 ℃ at a heating rate of 2 ℃/min under an air atmosphere, preserving heat for 15h, naturally cooling, grinding, washing with distilled water, and drying in a vacuum drying oven to obtain NaFe with a chemical formula of 0.33 Ni 0.33 Mn 0.33 O 2 An O3 type layered oxide sodium ion battery positive electrode material.
Application example 1
The positive electrode material prepared in example 1, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) were mixed according to a mass ratio of 8:1:1, mixing, pulping, coating on aluminum foil with thickness of 150 micrometers, vacuum drying, cutting into raw sheets with diameter of 10mm, and assembling into CR2032 type button cell by taking metal sodium sheets as negative electrodes, wherein the electrolyte is NaClO of 1M 4 Propylene Carbonate (PC) and 5wt.% fluoroethylene carbonate (FEC) additives, with a standard specific capacity of 1 c=200 mAh/g, with a charge-discharge current of 0.1C as the first turn.
Application example 2
Application example 2 differs from application example 1 only in that application example 2 uses the positive electrode material prepared in example 2, and otherwise is the same as application example 1.
Application example 3
Application example 3 differs from application example 1 only in that application example 3 uses the positive electrode material prepared in example 3, and otherwise is the same as application example 1.
Comparative application example 1
Comparative application example 1 differs from application example 1 only in that comparative application example 1 uses the positive electrode material prepared in comparative example 1, and otherwise is the same as application example 1.
Comparative application example 2
Comparative application example 2 differs from application example 2 only in that comparative application example 2 uses the positive electrode material prepared in comparative example 2, and otherwise is the same as application example 2.
Comparative application example 3
Comparative application example 3 differs from application example 3 only in that comparative application example 3 uses the positive electrode material prepared in comparative example 3, and otherwise is the same as application example 3.
Performance testing
XRD test
XRD testing was performed on the positive electrode materials prepared in examples 1 to 3, and XRD data of the positive electrode materials in examples 1 to 3 were subjected to refinement fitting by GASA software, and the refinement maps are shown in fig. 2, 3, and 4, respectively, wherein 2Theta (θ) on the abscissa represents the diffraction angle 2θ.
The crystal space group of the P2 type of example 1 was P63/mmc, and the standard PDF card was 054-0894 (red vertical line represents diffraction peak of the standard card). As can be seen from FIG. 4, the group of crystal spaces of the O3 type of example 3 is R-3m, and the standard PDF card is 054-0887 (blue vertical line represents diffraction peak of the standard card). The embodiment is perfectly compatible with standard PDF cards. The preparation method provided by the invention can well synthesize the P2 type, P2/O3 composite type and O3 type layered oxide characterization positive electrode material through fine fitting, and the perfect fitting degree of XRD crystal data can ensure that the single crystal material is prepared.
SEM observation
SEM microstructure observations were performed on the positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3, and the results are shown in fig. 5, in which fig. 5 (a), 5 (b), and 5 (c) are SEM images of the positive electrode materials of example 1, example 2, and example 3, respectively, and fig. 5 (d), 5 (e), and 5 (f) are SEM images of the positive electrode materials of comparative examples 1, 2, and 3, respectively. As can be seen from FIG. 5, the layered transition metal oxides of examples 1 to 3 were hexagonal block-shaped particles, the length direction dimension was about 500nm to 2. Mu.m, the particles were uniformly dispersed, and most of the particle surfaces had no apparent crystal face gap, namely, primary particles, which could be regarded as single crystal materials. The positive electrode materials obtained in comparative examples 1 to 3 were severe in particle agglomeration, different in size, and many crystal face traces were present between the particles. The special net egg-shaped structure and the alginate can well disperse single transition metal ions, and after calcination, the crystals are ensured to be sufficiently dispersed, and the monocrystal material can be obtained by sintering.
HRTEM test
HRTEM test was performed on the O3 type positive electrode material prepared in example 3, and the results are shown in fig. 6, wherein fig. 6 (a) is an HRTEM spectrum, and fig. 6 (b) is an electron selective diffraction pattern. As can be seen from fig. 6, under the high resolution transmission electron microscope, the lattice fringes are quite obvious and no multiphase is found, and at the same time, the electron selective diffraction pattern proves that example 3 is a single crystal material, and the (100), (113) and (013) planes are presented on the [031] crystal plane.
4. Cycle performance test
The CR2032 type button cell prepared in application examples 1-3 and comparative application examples 1-3 was subjected to cycle performance test, and the results are shown in FIGS. 7-9, respectively, and the cycle numbers on the abscissa in FIGS. 7-9 are the cycle numbers. As can be seen from FIGS. 7-9, the specific capacities of the first turns are 112mAh/g, 140mAh/g and 150mAh/g, respectively. The battery of application example 1 has a capacity retention rate of 75%, a specific capacity remaining of 70mAh/g, a capacity retention rate of 58% and a specific capacity remaining of 52mAh/g; the battery of application example 2 has a capacity retention rate of 80% and a specific capacity of 81mAh/g remaining; the capacity retention rate of the battery of comparative application example 2 was 60%, and the specific capacity remained at 60mAh/g; the battery of application example 3 has a capacity retention rate of 72% and a specific capacity of 89mAh/g remaining; the capacity retention rate of the battery of comparative application example 3 was 61%, and the specific capacity remained at 66mAh/g; the positive electrode material prepared from the transition metal salt and the sodium alginate can be applied to a sodium ion battery, so that the battery has good cycle performance.
5. Rate capability test
The CR2032 type button cell prepared in application examples 1-3 and comparative application examples 1-3 was subjected to rate performance test, and the results are shown in FIGS. 10-12, respectively, and the cycle numbers on the abscissa in FIGS. 10-12 are the cycle numbers. As can be seen from fig. 10 to 12, the capacities of application example 1 at (0.1, 0.5, 1, 2, 5, 10, 0.1C) magnifications are 102, 96, 72, 52, 40, 25, 114mAh/g, respectively; the capacities of comparative application example 1 at (0.1, 0.5, 1, 2, 5, 10, 0.1C) magnifications were 106, 90, 70, 55, 37, 10, 123mAh/g, respectively; application example 2 had capacities of 110, 91, 78, 65, 43, 24, 124mAh/g at (0.1, 0.5, 1, 2, 5, 10, 0.1C) magnifications, respectively; the capacities of comparative application example 2 at (0.1, 0.5, 1, 2, 5, 10, 0.1C) magnifications were 106, 89, 69, 55, 34, 11, 117mAh/g, respectively; application example 3 has capacities of 130, 117, 101, 82, 65, 38, 132mAh/g at (0.1, 0.5, 1, 2, 5, 10, 0.1C) magnifications, respectively; the capacities of comparative application example 3 at (0.1, 0.5, 1, 2, 5, 10, 0.1C) magnifications were 121, 103, 88, 76, 58, 15, 123mAh/g, respectively; the P2 type, P2/O3 composite type and O3 type layered transition metal oxide positive electrode materials prepared by the invention are proved to have good electrochemical performance under the 5C/10C multiplying power.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A positive electrode material is characterized by comprising a layered transition metal oxide, wherein the structural formula of the layered transition metal oxide is Na x MO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.48 and less than or equal to 1; and M is a transition metal element.
2. The positive electrode material according to claim 1, wherein when 0.48.ltoreq.x <0.75, the layered transition metal oxide is a P2-type layered oxide; when x is more than or equal to 0.75 and less than or equal to 0.89, the layered transition metal oxide is a P2/O3 composite layered oxide; when x is less than or equal to 0.89 and less than or equal to 1, the layered transition metal oxide is O3 type layered oxide.
3. The positive electrode material of claim 2, wherein M comprises at least one of Ni, mn, co, fe, cu, ti, nb.
4. The positive electrode material according to claim 3, wherein the layered transition metal oxide has a structural formula of Na x Fe y Ni z Mn 1-y-z O 2 ，0.48≤x≤1；0≤y≤1，0≤z≤1。
5. The positive electrode material according to claim 4, wherein the layered transition metal oxide is of a single crystal structure; and/or, the layered transition metal oxide is a hexagonal block-shaped particle.
6. The method for producing a positive electrode material according to any one of claims 1 to 5, comprising the steps of:
and mixing transition metal salt and sodium alginate, reacting, and calcining to obtain the anode material.
7. The method of manufacturing according to claim 6, comprising the steps of:
(1) Mixing transition metal salt solution and sodium alginate solution, and reacting to obtain a precursor;
(2) Calcining the precursor obtained in the step (1) to obtain the positive electrode material.
8. The method according to claim 6, wherein the molar ratio of the transition metal salt to the sodium alginate is 1:0.35-2.2.
9. The method according to claim 6, wherein the reaction time is 0.5 to 24 hours; the calcination temperature is 650-1050 ℃, and the calcination time is 4-24h.
10. A battery comprising the positive electrode material according to any one of claims 1 to 5.
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