GB2618967A - Preparation method for p2-type manganese-based sodium-ion battery positive electrode material - Google Patents
Preparation method for p2-type manganese-based sodium-ion battery positive electrode material Download PDFInfo
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- GB2618967A GB2618967A GB2313934.8A GB202313934A GB2618967A GB 2618967 A GB2618967 A GB 2618967A GB 202313934 A GB202313934 A GB 202313934A GB 2618967 A GB2618967 A GB 2618967A
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- sodium
- manganese
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- positive electrode
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- 239000011572 manganese Substances 0.000 title claims abstract description 32
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 31
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000011734 sodium Substances 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- -1 sodium manganate trioxalate Chemical compound 0.000 abstract 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IKULXUCKGDPJMZ-UHFFFAOYSA-N sodium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Na+] IKULXUCKGDPJMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NUVDSAKVXWKOAW-UHFFFAOYSA-L dichloronickel;ethanol Chemical compound CCO.Cl[Ni]Cl NUVDSAKVXWKOAW-UHFFFAOYSA-L 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 101150050740 ino1 gene Proteins 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A preparation method for a P2-type manganese-based sodium-ion battery positive electrode material, comprises: adding manganese dioxide to an oxalic acid solution for reaction to obtain a first reaction solution; adding a sodium hydroxide solution to the first reaction solution for reaction to obtain a second reaction solution; performing ice bath on the second reaction solution, adding a doped metal-containing alcohol solution for alcohol precipitation, and performing solid-liquid separation to obtain a precipitate; and mixing the precipitate with a manganese source, and grinding and calcining the mixture to obtain the P2-type manganese-based sodium-ion battery positive electrode material. According to the method, sodium manganate trioxalate is prepared by means of a complexation reaction of oxalic acid and manganese dioxide, and neutralization of sodium hydroxide. When the sodium-ion battery positive electrode material is prepared, a precipitate containing sodium manganate trioxalate is used as a sodium source, and no additional sodium source needs to be supplemented during sintering, so that the problem that Na+ in an external sodium source is difficult to completely enter a crystal lattice due to a large ionic radius is avoided, the sodium residues on the surface of the material are reduced, and the electrochemical performance of the material is further improved.
Description
PREPARAtION METHOD FOR P2-TYPE MANGANESE-BASED SODIUM-ION
BATTERY POSITIVE ELECTRODE MATERIAL
HELD
[00011 The present disclosure belongs to the technical field of sodium-ion batteries, and specifically relates to a preparation method of a P2-type manganese-based positive electrode materia.1 for sodium-ion battery.
BACKGROUND
100021 lithium-ion batteries have been widely used in fields such as portable eiectronlc T.is and electric vehicles, and have d great success and rapid growth. However, the low source reserves of lithium lead to the rising cost of lithium-ion batteries, and sodium-ion batteries are expected to replace lithium-ion batteries in large-scale energy storage devices. Among the many positive electrode materials for sodium-ion batteries, layered transition metal oxides" especially sodium manganese oxides, have attracted extensive attention from researchers due to their advantages in" for example, high specific capacity and operating voltage, easy preparation, environmental friendliness, non-toxicity, and low cost [0003] Layered sodium manganese oxides are ne of the positive rode materials for sodium-ion batteries, and mainly divided into two structures. P2 phase and 03 phase. Compared with the 03 phase structure, the P2 phase structure has higher ionic conductivity and lower diffusion barrier Therefore, P2-type manganese-based layered oxide is a promising positive electrode material for sodium-ion batteries.
[0004] P2-Na0 67MnO2 material has excellent electrochemical properties that the theoretical specific capacity is about 173 mAhlg and the average operating voltage is up to 3.8V, which has attracted extensive attention from researchers in related fields. P2-Na0 671VM02 material has a simple synthesis process. Compared with most P2 phase materials, P2-Na0.67Mn02 material does not require high temperature quenching after sintering to ensure that the material does not undergo P2-P3 phase transition; by natural cooling after sintering, P2 structure can be obtained, which is conducive to the wide application of materials. P2-Nao.6rMn02, material will undergo P2-02 transition when it is charged above 4.2V Besides, there are many factors such as Nat vacancy ordered structure in P2-type layered oxides, resulting in poor electrochemical stability. Element doping is an effective means to reduce the order degree of Na vacancies, improve the diffusion ability of Na'. improve the rate capability of materials, inhibit phase transition and improve cycling stability.
[00051 Doping and modifying the material can improve the lattice structure of the electrode material,improve the thermal stability of the material, and increase the ion diffusion capacity of the material to reduce the capacity loss during cycling,thereby enhancing the overall electrochemical performance of sodium-ion batteries.
[00061 However, the currcnlly reported doping and modification techniques generally use manganese source, sodium source and doping element to perform solid phase sintering together, which makes it difficult for doping element to enter the NaMn02 crystal structure or makes the amount of doping element entering the structure small. it is difficult to achieve the ideal function of stabilizing the crystal structure.
[00071 Furthermore, compaed with the sintering 11 n battery precursors, since the radius of Li ions is smaller than that of Na in the one--step high--temperature solid phase synthesis process, Li is more likely to enter the material lattice, while Na is difficult to completely enter the interior of the lattice due to the larger ionic radius, so that a large amount of sodium compounds remains on the surface of the material, which affects the electrochemical performance of the material.
SUMMARY
[00081 The present disclosure aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present disclosure provides a preparation method of a P2-type manganese-based positive electrode material for sodium-ion battery; which can improve the doping effect of doping metal and the intercalation of sodium ions, thereby improving the stability and electrochemical performance of the material.
[0009] According to one aspect of the present disclosure, preparation method of a P2-type manganese-based positive electrode material for sodium-ion battery is proposed, comprising
_ _
steps of 100101 Si: adding manganese dioxide to an oxalic acid solution, and reacting at a certain temperature to obtain a. first reaction solution, 100111 52: adding a sodium hydroxide solutio react on solution, reacting solution pH is stable at 4.8-5.2 to obta. ond action solution [0012] 53: subjecting the second reaction solution to an ice bath, adding an alcohol solution containing doping metal for alcohol precipitation, and performing solid-liquid separation to obtain a precipitate; and [00131 54: mixing the precipitate manganese source, grinding, and then ca obtain the P2-type manganese-based positive rode material fin sodium-ion battery [00141 In some embodiments of the present disclosure, in step S1, a concentration. of tLte oxahc acid solution is 2-5 mol/L, a solid-liquid ratio of an added amount of the manganese dioxide to the oxalic acid solution is (25-80) g: I L. [0015] In some embodiments of the present drelt carried1, the reacting is ut at a temperature of 70-90°C 1.00161 In smile embodiments of the present disclosure, in step 52, a concentration of the sodium hydroxide solution is 0.5-2.0 mott.
[0017] In some embodiments of the present disclosure,n step 53, the doping metal is at eas one of copper, nickel and magnesium.
[0018] In some embodiments of the present disclosure, in step S3, the alcohol solution containing doping metal is an alcohol solution of at least one of cupric chloride, nickel chloride, magnesium chloride and magnesium bromide; optionally, the alcohol in the alcohol solution is ethanol.
[0019] In sonic embodiments of the present disclosure, in step 53, a concentration doping metal in the alcohol solution containing doping metal is 0.05-0.35 inol/L, and an added amount of the alcohol solution containing doping metal is 0.8-1.2 times a volume of the oxalic acid solution.
[0020] In some embodiments of the present disclosure, in step S3, after the solid-liquid separation, it further comprises washing the precipitate. Preferably, the solid-liquid separation and washing operation are both completed under shading conditions, and absolute ethanol is used for the washing.
[00211 In some embodiments of the present disclosure, in step S4, the manuanese source is at least one of manganese dioxide, manganese oxalate, manganese acetate and manganese carbonate.
[0022] In some ernbodunerits of esent disciosu S4, in a material after the MIX LI an element molar ratio of sodium to manganese is [0023] In some embodiments of the present disclosure, in step S4, the calcining is carried out at a temperature of 800-1000T [00241 In some embodiments of the present disclosure, in step S4, the calcining is carried out for 0-24 h. [0025] According to a preferred embodiment of the present disclosure, it has at least the following beneficial effects: [0026] -1 In the present disclosure, so ornananate is oiriplexation reaction between oxalic acid and manganese dioxide and neutralization by sodium hydroxide. The reaction equation is as follows: 2Mn07+71-1-2C204=2H3rkln(C.204)314-2CO24-4IT20, 14311Mn(C204)31143Na011.-Na5[Mn(C204)3]-1-31-1-20. In the preparation of the positive electrode material for sodium-ion battery, the precipitate containing sodium trioxalatomanganate is used as the sodium source. During sintering, there is no need to supplement the sodium source additionally, thereby avoiding the problem that Na' in the external sodium source is difficult to completely enter the interior of the lattice due to the large ionic radius, reducing the residual sodium on the surface of the material, and further improving the electrochemical performance of the material.
[0027] 2. At the same time of precipitation of sodium trioxalatomanganate using the alcohol solution containing doping metal, the generated oxalate and sodium trioxalatomanizanate are co-precipitated, so that sodium element and doping metal enter inside the crystal together [0028] 3, The inLroduction of doping metal further stabilizes the internal structure, overcomes the problems of uneven doping of elements and easy collapse of the lattice during id state sintering in the prior art, and further improves the specific capacity, cycle performance and rate capability of the positive electrode material for sodium-ion batteries.
BRIEF DESCRIPTION OF DRAWINGS
[0029] The present disclosure will be further illustrated below in coi unet n with the accompanying drawings and examples, in which: [0030] FIG I is a SEM image of the P2-type manganese-based positive electrode material for sodium-ion battery prepared in Example 1 of the present disclosure.
DETAILED DESCRIPTION
[0031] The concept of the present disclosure and the technical effects produced thereby will be clearly and completely described below in conjunction with the examples" so as to fully understand the purpose, characteristics and effects of the present disclosure. Obviously the described examples are only a part of the embodiments of the present disclosure, rather than all the embodiments. Based on the embodiments of the present disclosure, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of protection of the present disclosure.
Example I
[0032] in this example, a P2-type manganese-based positive electrode material for sodium-ion battery is prepared. The the specific process is as follows: [00331 (1) 100 rnI, of oxahc acid solution with a concentration prepared; 100341 (2) 2.5 g of manganese dioxide was added to the oxalic acid solution, and the reaction temperature was controlled 70°C until tile solid was completely dissolved to obtain a first reaction solution, [00351 (3) After the reaction in step (2) was completed, 2.0 mon so n hydroxide solutk, was added immediately untji the pH at the solution was 4.8-5,2. After the reaction was completed, a second reaction solution was obtained and the second reaction solution was subjected to an ice bath; [00361 (4) 12.0 int of magnesuim chloride ethanol solution with a concentration of 0.05 mo11.1. was prepared. and added to the second reaction solution under ice bath in step (3) for alcohol precipitation, wherein the ethanol was absolute ethanol; [0037] (5) Solid-liquid se was pertornied in the dark, and the obta iee precip. vas washed with absolute ethanol; and 100381 (6) The washed precipitate was n 4th manganese dioxide and then ground. In the material after mixing, the element molar ratio of sodium to manganese was 1:3. The material was calcined at 800°C for 24 h to obtain a P2-type manganese-based positive electrode material for sodium-ion battery.
Example 2
[0039] In this example, a P2-type manganese-based positive electrode material for sodium-ion battery is prepared. The the specific;process is as follows: [00401 (1) 100 mi. of oxalie acid solution with a concentration of 4 ino1/1_, was prepared; [004i] (2) 5.0 g of manganese dioxide was added to the oxalic acid solution, and the reaction temperature was controlled at 80°C until the solid was completely dissolved to obtain a first reaction solution; [00421 (3) After the reaction step (2) was completed, 1.0 moll. sodium hydroxide solution was added immediately until the pH of the solution was 4.8-5.2. After the reaction was completed, a second reaction solution was obtained and the second reaction solution was subjected to an ice bath.
100431 (4) 100 niL of nickel chloride ethanol caution with a concentration of 0,07 molt was and added to the second reaction solution under ice bath in step (3) for alcohol precipitation, wherein the ethanol was absolute ethanol; [0044] separation /as perforimed in the dark, and the obtained precipitate was washed with absolute ethanol; and [0045] (6) The washed precipitate was mixer with 'manganese oxalate and then ground. In the material after mixing, the element molar ratio of sodium to manganese was 2:3. The material was ined at 900°C for 18 h to obtain a P2-type manganese-based positive electrode material for battery.
Example 3
100461 In this example, a P2-type manganese-based positive electrode material for -4,ti battery is prepared. The specific process is as follows: 100471 (1) 100 nth of oxalic acid solution with a concentration or S ntol/Las prepared; [0048] (2) 8.0 g of manganese dioxide was added to the oxalic acid solution, and the reaction temperature was controlled at 90°C until the solid was completely dissolved to obtain a first reaction solution; [0049] (3) After the reaction in step (2) was completed, 2.0 moll. sodium hydroxide solution was added immediately until the pEl of the solution was 4.8-5.2. After the reaction was completed, a second reaction solution was obtained and the second reaction solution was subjected to an ice bath; [0050] (4) 80 rnL of cupric lanai solar)f with a concentration of 0.35 mail, was prepared, and added to the second reaction solution under ice bath in step (3) for alcohol precipitation, 'wherein the ethanol was absolute ethanol; [005l1 (5) separation was performed in the dark, and the obtained precipitate was washed with absolute ethanol; and [0052] (6) The washed precipitate was mixed with manganese carbonate and then ground. In the material after mixing, the element molar ratio of sodium to manganese was 1: I. The material was calcined at 1000°C for 10 h to obtain a P2-type manganese-based positive electrode material for sodium-ion battery.
Comparative Example 1 [0053] In this comparative example, a P2-type manganese-based positive electrode material for sodium-ion battery was prepared. This comparative example differs from Example 2 in that a sodium source and a manganese source were directly sintered in solid state without doping. The ific process is as follows: 100541 Manganese oxalate and sodiann oxalate were mixed according to an element molar ratio of sodium to manganese being 2:3, then ground, and calcined at 900"C for 18 h to obtain a manganese-based positive electrode material for sodium-ion battery.
lest example
[0055] The positive electrode materials for sodium-ion battery prepared in Examples Comparative Example 1 were assembled into sodium-Hon half cells respectively. In a voltage range of 2.0-3 8 V at a rate of 0.8C, the capacity per grant at the first charge and discharge and the capacity per gram after 100 cycles of charge and discharge were tested, and the results are shown in Table 1.
Table 1 Electrochenrcal properties of positive electrode materials for sodium-ion batierie, [0056] It can be seen from Table I that the capacity per gram at the first charge and discharge and cycle performance of the positive electrode material for sodium-ion battery obtained by direct solid phase sintering in Comparative Example I were significantly lower than those of the Examples This is because in the examples, the precipitate containing sodium trioxalatomanganate is used as the sodium source, and the co-precipitation of sodium trioxalatomanganate and the metal-doped oxalate enables the sodium element and the doped metal to enter inside the crystal together, avoiding the uneven doping of element and the lattice Capacity per gram at the first charge 11 and discharge at 0.8C rate mAh/a Capacity per gram after 100 times of charge and discharge inAh/g Example 1 147.4 134.8 Example 2 158.3 145.1 Example 3 159.6 146.7 (onmarative 128.4 86.7
Example
collapse during sintering, improving the specific capacity and cycle performance of the positive electrode material -odium-ion battery.
100571 The embodiments of the present disclosure have been described in detail above conjunction with the drawings. However, the present disclosure is not limited to the above-mentioned embodiments, and various modifications can be made without departing from the purpose of the present disclosure within the scope of knowledge possessed by those of ordinary skill in the art, in addition, in the case of no conflict, the embodiments of the present disclosure and the features in the embodiments may be combined with each other.
Claims (10)
- CLAIMSI. A preparation method of a P2-type manganese -based positive electrode material for sodium-ion battery, comprising steps of: Si:adding manganese dioxide to an oxalic acid solution, and reacting a certain temperature to obtain a first reaction solution: 52: adding a sodium hydroxide solution to the first solution,ion and reacting until solution pH is stable at 4.8-5.2 to obtain a. second reaction solution; 53: subjecting the second reaction solution to an ice bath, adding an alcohol solutio containing doping metal for alcohol precipitation, and performing solid-liquid separation to obtain a precipitate.; and 54: mixing the precipitate with a manganese source, grinding, and then calcium, to obtain the P2-type manganese-based positive electrode material feiir sodium-ion battery.
- 2. The preparation method according to claim 1, wherein in step Si a concentration of the oxalic acid solution is 2-5 mon.
- 3. The preparation method accon.ding to claim I, wherein in step Si, the reacting is carried out at a temperature of 70-90°C.
- 4. The preparation method according claim 1, where in step Si, a concentration of the sodium hydroxide solution is 0.5-2.0 mo111-
- 5. The preparation method according to claim I wherein step S3 the doping metal is at least one of copper, nickel and magnesium.
- 6 The preparation method according to claim I or 5 wherein in step 53, tile alcohol sciatic containing doping metal isan alcohol solution of at least one of cupric chloride, nickel chloride, magnesium chloride and magnesium bromide, optionally, the alcohol in the alcohol solution is ethanol.
- 7. The preparation method accordtng to claim 1, wherein in step S3, a concentration of the ig metal in the alcohol solution containing doping metal is 0.05-0.35.ino171.." and an added nt of the alcohol solution containing doping metal is 0.8-1.2 times a volume of the oxalic solution.
- 8. The preparation method according to claim 1, wherein in step S4, the manganese source is at least one of manganese dioxide, manganese oxalate, manganese acetate and manganese carbonate.
- 9. The preparation method according to claim 1, wherein in step S4, in a material mixing, an element molar ratio of sodium to manganese is ( I-3): 3.
- 10. The preparation method according to clai step S4, the calcir g is out at a temperature of 800-100091
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| PCT/CN2022/114551 WO2023098168A1 (en) | 2021-11-30 | 2022-08-24 | Preparation method for p2-type manganese-based sodium-ion battery positive electrode material |
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| WO2014115772A1 (en) * | 2013-01-23 | 2014-07-31 | 学校法人東京理科大学 | Combined metal oxide, positive-electrode active substance for sodium secondary cell, positive electrode for sodium secondary cell, and sodium secondary cell |
| US20150004491A1 (en) * | 2013-06-28 | 2015-01-01 | Nichia Corporation | Positive-electrode active material for non-aqueous secondary battery and method for producing the same |
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| CN111180706A (en) * | 2020-01-08 | 2020-05-19 | 太原理工大学 | Preparation method of sodium titanium manganese acid sodium as positive electrode material of sodium ion battery |
| CN114229908A (en) * | 2021-11-30 | 2022-03-25 | 广东邦普循环科技有限公司 | Preparation method of P2 type manganese-based sodium ion battery positive electrode material |
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| CN105932260B (en) * | 2016-06-30 | 2020-10-30 | 中南大学 | Sodium ion battery oxide positive electrode material and preparation method and application thereof |
| CN107591531A (en) * | 2017-09-25 | 2018-01-16 | 华南师范大学 | A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application |
| CN111224093B (en) * | 2019-10-12 | 2022-05-27 | 南方科技大学 | Electrode material with manganese concentration gradient, preparation method thereof and sodium-ion battery |
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| WO2014115772A1 (en) * | 2013-01-23 | 2014-07-31 | 学校法人東京理科大学 | Combined metal oxide, positive-electrode active substance for sodium secondary cell, positive electrode for sodium secondary cell, and sodium secondary cell |
| US20150004491A1 (en) * | 2013-06-28 | 2015-01-01 | Nichia Corporation | Positive-electrode active material for non-aqueous secondary battery and method for producing the same |
| US20180205081A1 (en) * | 2015-07-15 | 2018-07-19 | Toyota Motor Europe | Sodium layered oxide as cathode material for sodium ion battery |
| CN109686969A (en) * | 2018-12-14 | 2019-04-26 | 北京化工大学 | A kind of sodium-ion battery of the preparation and application of stratiform transition metal oxide the material material |
| CN111180706A (en) * | 2020-01-08 | 2020-05-19 | 太原理工大学 | Preparation method of sodium titanium manganese acid sodium as positive electrode material of sodium ion battery |
| CN114229908A (en) * | 2021-11-30 | 2022-03-25 | 广东邦普循环科技有限公司 | Preparation method of P2 type manganese-based sodium ion battery positive electrode material |
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