CN115849453A - Ternary codoped manganese dioxide material and preparation method and application thereof - Google Patents
Ternary codoped manganese dioxide material and preparation method and application thereof Download PDFInfo
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- CN115849453A CN115849453A CN202211627723.5A CN202211627723A CN115849453A CN 115849453 A CN115849453 A CN 115849453A CN 202211627723 A CN202211627723 A CN 202211627723A CN 115849453 A CN115849453 A CN 115849453A
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- manganese dioxide
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011572 manganese Substances 0.000 claims abstract description 27
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 37
- 238000000498 ball milling Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 229940093474 manganese carbonate Drugs 0.000 claims description 17
- 235000006748 manganese carbonate Nutrition 0.000 claims description 17
- 239000011656 manganese carbonate Substances 0.000 claims description 17
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 17
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 17
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 12
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 10
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 9
- 229940078494 nickel acetate Drugs 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 claims description 9
- ZZCONUBOESKGOK-UHFFFAOYSA-N aluminum;trinitrate;hydrate Chemical compound O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZZCONUBOESKGOK-UHFFFAOYSA-N 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 8
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 8
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 6
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 2
- 239000007891 compressed tablet Substances 0.000 claims description 2
- 239000003826 tablet Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
- 235000011128 aluminium sulphate Nutrition 0.000 description 5
- 239000001164 aluminium sulphate Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 3
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 3
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QMGYPNKICQJHLN-UHFFFAOYSA-M Carboxymethylcellulose cellulose carboxymethyl ether Chemical compound [Na+].CC([O-])=O.OCC(O)C(O)C(O)C(O)C=O QMGYPNKICQJHLN-UHFFFAOYSA-M 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a ternary codoped manganese dioxide material and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a ternary codoped metal source and a manganese source, calcining, and then crushing to obtain the ternary codoped manganese dioxide cathode material; the ternary co-doped metal source comprises a titanium source, an aluminum source and a nickel source. The invention adopts a synthesis mode of ternary metal co-doped manganese dioxide, improves gram capacity and capacity utilization rate, and improves the platform potential of the manganese dioxide, thereby increasing the energy density of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium-manganese dioxide battery anode materials, and relates to a ternary codoped manganese dioxide material, and a preparation method and application thereof.
Background
In a lithium primary battery, a light metal such as lithium is used as a negative electrode active material, and manganese dioxide is used as a positive electrode active material. Such a lithium primary battery has characteristics that are not possessed by other primary batteries, such as a high voltage and a high energy density, a small self-discharge, and a very long storage life. Therefore, lithium primary batteries have been used in various electronic devices. Among them, manganese dioxide is used as a positive electrode active material because it is inexpensive and abundant. When manganese dioxide is used as a positive electrode active material of a lithium primary battery, electrolytic manganese dioxide having excellent discharge performance and long-term storage performance is generally used.
CN 101999186A provides an electrolytic manganese dioxide for lithium primary battery, which is characterized in that: the sodium content is 0.05 to 0.2 mass%, and the pH value is 5 to 7 as measured by JIS-K-1467. By using such electrolytic manganese dioxide as a positive electrode active material, a lithium primary battery having not only excellent initial discharge characteristics but also excellent long-term discharge characteristics can be provided.
CN 111005031A provides a method for preparing doped modified electrolytic manganese dioxide, which comprises the following steps: 1) Adding acid-insoluble powder into an acid electrolyte containing manganese sulfate to obtain an electrolytic suspension solution; 2) Electrolyzing the electrolytic suspension solution; 3) Stripping an electrolysis product from an electrolytic anode, rinsing, grinding and screening to obtain the doped modified electrolytic manganese dioxide. The preparation method of doped modified electrolytic manganese dioxide provided by the invention is to prepare doped electrolytic manganese dioxide by electrolyzing an acidic manganese sulfate solution containing a certain content of acid-insoluble metal oxide powder by a suspension electrolysis method. So that the doping material is positioned in the electrolytic manganese dioxide particles, and the method has simple process and is suitable for industrial production.
However, the capacity utilization rate of about 82% of the commercial lithium-manganese dioxide battery based on electrolytic manganese dioxide greatly limits its application in high-end fields. The discharge platform of the electrolytic manganese dioxide material is low, which is not beneficial to the improvement of the energy density of lithium-manganese dioxide, and limits the application of the electrolytic manganese dioxide material in the aspect of power type electronic products.
Therefore, it is necessary to develop a new method for preparing manganese dioxide cathode material to solve the problem of low capacity utilization rate of electrolytic manganese dioxide and improve the electrochemical performance of the material.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a ternary co-doped manganese dioxide material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a ternary co-doped manganese dioxide material, which comprises the following steps:
mixing a ternary codoped metal source and a manganese source, calcining, and then crushing to obtain the ternary codoped manganese dioxide cathode material;
the ternary co-doped metal source comprises a titanium source, an aluminum source and a nickel source.
The invention adopts a synthesis mode of ternary metal co-doped manganese dioxide, improves gram capacity and capacity utilization rate, and improves the platform potential of the manganese dioxide, thereby increasing the energy density of the battery.
The doped titanium source can improve the capacity of the battery, the doped aluminum source is beneficial to improving the discharge platform potential of the battery, and the doped nickel source can effectively reduce the cost.
Preferably, the titanium source comprises titanium dioxide.
Preferably, the titanium dioxide comprises rutile titanium dioxide.
Preferably, the aluminium source comprises any one or a combination of at least two of aluminium nitrate, aluminium nitrate hydrate, aluminium chloride hydrate, aluminium sulphate or aluminium sulphate hydrate, typical but non-limiting combinations include a combination of aluminium nitrate and aluminium nitrate hydrate, a combination of aluminium nitrate hydrate and aluminium chloride, a combination of aluminium chloride and aluminium chloride hydrate, a combination of aluminium chloride hydrate and aluminium sulphate, a combination of aluminium sulphate and aluminium sulphate hydrate, a combination of aluminium nitrate, aluminium nitrate hydrate and aluminium chloride, a combination of aluminium nitrate hydrate, aluminium chloride and aluminium chloride hydrate, a combination of aluminium chloride, aluminium chloride hydrate and aluminium sulphate, a combination of aluminium chloride hydrate, aluminium sulphate and aluminium sulphate hydrate.
Preferably, the nickel source comprises any one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, or nickel oxyhydroxide or a combination of at least two of them, typical but non-limiting combinations include a combination of nickel nitrate and nickel acetate, a combination of nickel acetate and nickel sulfate, a combination of nickel sulfate and nickel chloride, a combination of nickel chloride and nickel sulfamate, a combination of nickel sulfamate and nickel bromide, a combination of nickel bromide and nickel oxyhydroxide, a combination of nickel nitrate, nickel acetate and nickel sulfate, a combination of nickel acetate, nickel sulfate and nickel chloride, a combination of nickel sulfate, nickel chloride and nickel sulfamate, a combination of nickel chloride, nickel sulfamate and nickel bromide, a combination of nickel sulfamate, nickel bromide and nickel oxyhydroxide.
Preferably, the manganese source comprises a manganese salt and/or manganese dioxide.
Preferably, the manganese salt comprises any one of manganese carbonate, manganese hydroxide or manganese oxalate or a combination of at least two of them, typically but not limited to a combination of manganese carbonate and manganese hydroxide, manganese hydroxide and manganese oxalate, manganese carbonate and manganese oxalate, or a combination of manganese carbonate, manganese hydroxide and manganese oxalate.
Preferably, the manganese dioxide is synthesized by a chemical method and/or an electrolytic method.
Preferably, the molar amount of the titanium source is 3 to 4mol% of the molar amount of the manganese source, and may be, for example, 3mol%, 3.2mol%, 3.5mol%, 3.8mol%, or 4mol%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the molar amount of the aluminum source is 5 to 7mol% of the molar amount of the manganese source, and may be, for example, 5mol%, 5.5mol%, 6mol%, 6.5mol%, or 7mol%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the molar amount of the nickel source is 2 to 3mol% of the molar amount of the manganese source, and may be, for example, 2mol%, 2.2mol%, 2.5mol%, 2.8mol%, or 3mol%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, ball milling and tabletting are also included before calcination.
Preferably, the ball-milling has a ratio of (4 to 6) to 1, which may be, for example, 4.
Preferably, the rotation speed of the ball mill is 500 to 600rpm, for example, 500rpm, 520rpm, 550rpm, 580rpm or 600rpm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the frequency of the ball milling is 30 to 50Hz, for example 30Hz, 35Hz, 40Hz, 45Hz or 50Hz, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the ball milling time is 20 to 25 hours, for example 20 hours, 21 hours, 22 hours, 23, 24 hours or 25 hours, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the pressure of the compressed tablet is 10 to 50 tons, for example, 10 tons, 20 tons, 30 tons, 40 tons or 50 tons, but is not limited to the recited values, and other values in the numerical range not recited are also applicable, preferably 30 to 50 tons.
Preferably, the pellet has a diameter of 10 to 15mm, for example 10mm, 11mm, 12mm, 13mm, 14mm or 15mm, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the thickness after tabletting is 1.6 to 2mm, for example 1.6mm, 1.7mm, 1.8mm, 1.9mm or 2mm, but is not limited to the values listed, and other values within the range of values not listed apply equally, preferably 1.8 to 2mm.
The purpose of using a tablet in the present invention is to allow better solid phase diffusion.
Preferably, the calcination temperature is 400-420 ℃, for example 400 ℃, 405 ℃, 410 ℃, 415 ℃ or 420 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the calcination is carried out for a period of time of 24 to 48 hours, for example 24 hours, 30 hours, 35 hours, 40 hours or 48 hours, but not limited to the values listed, and other values not listed within the numerical ranges are equally applicable.
Preferably, the calcining further comprises crushing and ball milling.
Preferably, the particle size of the ball milled material is 10 to 15 μm, for example 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the time of the ball milling after calcination is 10 to 15 hours, for example 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the frequency of the ball milling after calcination is (4 to 6): 1, which can be, for example, 4.
Preferably, the rotational speed of the ball mill after calcination is in the range of 500 to 600rpm, for example 500rpm, 520rpm, 550rpm, 580rpm or 600rpm, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the frequency of the ball milling after calcination is in the range of 30 to 50Hz, for example 30Hz, 35Hz, 40Hz, 45Hz or 50Hz, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
As a preferable technical solution of the preparation method of the first aspect of the present invention, the preparation method comprises the steps of:
mixing a titanium source, an aluminum source, a nickel source and a manganese source, and then carrying out first ball milling for 20-25 h at the rotating speed of 500-600 rpm and the frequency of 30-50 Hz, wherein the ball-to-material ratio is (4-6) to 1; tabletting the first ball-milled material under 10-50 tons of pressure to obtain flakes with the diameter of 10-15 mm and the thickness of 1.6-2 mm; calcining the sheet materials at 400-420 ℃ for 24-48 h, then crushing, and carrying out second ball milling treatment at the rotating speed of 500-600 rpm and the frequency of 30-50 Hz for 10-15 h until the particle size is 10-15 mu m to obtain the ternary co-doped manganese dioxide cathode material;
the titanium source is rutile titanium dioxide, and the molar weight of the titanium source is 3-4 mol% of that of the manganese source;
the aluminum source is any one or the combination of at least two of aluminum nitrate, aluminum nitrate hydrate, aluminum chloride hydrate, aluminum sulfate or aluminum sulfate hydrate; the molar weight is 5-7 mol% of the molar weight of the manganese source;
the nickel source comprises any one or the combination of at least two of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide or nickel protoxide; the molar weight is 2-3 mol% of the molar weight of the manganese source;
the manganese source comprises a manganese salt and/or manganese dioxide; the manganese salt comprises any one or a combination of at least two of manganese carbonate, manganese hydroxide or manganese oxalate; the synthesis mode of the manganese dioxide comprises a chemical method and/or an electrolytic method.
In a second aspect, the invention provides a ternary codoped manganese dioxide material, and the ternary codoped manganese dioxide cathode material is obtained according to the preparation method of the first aspect.
Preferably, the chemical formula of the ternary co-doped manganese dioxide cathode material is MnTi x Al y Ni z O 2 Wherein x is in the range of 0.03 to 0.04, for example 0.03, 0.032, 0.035, 0.038 or 0.04, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
y is in the range of 0.05 to 0.07, for example 0.05, 0.055, 0.06, 0.065 or 0.07, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
z is in the range from 0.01 to 0.03, and can be, for example, 0.01, 0.015, 0.02, 0.025 or 0.03, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
In a third aspect, the invention provides a positive plate, wherein the positive plate contains the ternary co-doped manganese dioxide material according to the second aspect.
Preferably, the positive electrode sheet comprises a ternary codoped manganese dioxide material, a conductive agent and a binder, wherein the mass ratio is (7-9): (0.5-1.5), and the mass ratio can be, for example, 7.
In a fourth aspect, the invention provides a battery, which is characterized in that the battery contains the ternary codoped manganese dioxide material according to the second aspect or the positive plate according to the third aspect.
By the technical scheme, the invention has the following beneficial effects:
the invention adopts a synthesis mode of ternary metal co-doped manganese dioxide, improves gram capacity and capacity utilization rate, and improves the platform potential of the manganese dioxide, thereby increasing the energy density of the battery.
Drawings
FIG. 1 is a scanning electron micrograph of a ternary codoped manganese dioxide material described in example 1.
FIG. 2 is a scanning electron micrograph of the ternary codoped manganese dioxide material described in example 2.
FIG. 3 is a scanning electron micrograph of the ternary codoped manganese dioxide material described in example 3.
FIG. 4 is a scanning electron micrograph of the ternary codoped manganese dioxide material described in example 4.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
This example provides a ternary co-doped manganese dioxide material MnTi 0.037 Al y0.05 Ni 0.01 O 2 The preparation method comprises the following steps:
after rutile titanium dioxide, aluminum nitrate, nickel nitrate and manganese carbonate are mixed, first ball milling is carried out for 24 hours at the rotating speed of 580rpm and the frequency of 45Hz, and the ball-to-material ratio is 5; tabletting the material subjected to the first ball milling under the pressure of 40 tons to obtain sheet materials with the diameter of 12mm and the thickness of 1.8 mm; calcining the sheet materials at 410 ℃ for 30h, then crushing, and carrying out second ball milling treatment at the rotating speed of 580rpm and the frequency of 45Hz for 12h to obtain the ternary codoped manganese dioxide cathode material, wherein a scanning electron microscope picture is shown in figure 1.
Wherein the molar weight of the rutile type titanium dioxide is 3.7mol percent of the molar weight of the manganese carbonate; the molar weight of the aluminum nitrate is 5mol percent of that of the manganese carbonate; the molar weight of the nickel nitrate is 2-3 mol% of that of the manganese carbonate.
Example 2
This example provides a ternary co-doped manganese dioxide material MnTi 0.03 Al 0.05 Ni 0.02 O 2 The preparation method comprises the following steps:
after rutile titanium dioxide, aluminum chloride, nickel sulfamate and electrolytic manganese dioxide are mixed, first ball milling is carried out for 20 hours at the rotating speed of 500rpm and the frequency of 50Hz, and the ball-to-material ratio is 4; tabletting the material subjected to the first ball milling under the pressure of 30 tons to obtain a sheet material with the diameter of 10mm and the thickness of 1.6 mm; calcining the sheet materials at 400 ℃ for 48h, then crushing, and carrying out second ball milling treatment at the rotating speed of 500rpm and the frequency of 50Hz for 10h to obtain the ternary co-doped manganese dioxide cathode material, wherein a scanning electron microscope image is shown in FIG. 2;
wherein the molar weight of the rutile type titanium dioxide is 3mol percent of the molar weight of the electrolytic manganese dioxide; the molar weight of the aluminum chloride is 5mol percent of the molar weight of the electrolytic manganese dioxide; the molar amount of nickel sulfamate was 2mol% of the molar amount of electrolytic manganese dioxide.
Example 3
This example provides a ternary co-doped manganese dioxide material MnTi 0.04 Al 0.06 Ni 0.01 O 2 The preparation method comprises the following steps:
after rutile titanium dioxide, aluminum sulfate, nickel sulfate and manganese hydroxide are mixed, first ball milling is carried out for 25 hours at the rotating speed of 600rpm and the frequency of 30Hz, and the ball-to-material ratio is 4; tabletting the first ball-milled material under 50 tons of pressure to obtain 15 mm-diameter and 2 mm-thickness flakes; calcining the sheet materials at 420 ℃ for 24 hours, then crushing, and carrying out second ball milling treatment at the rotating speed of 600rpm and the frequency of 30Hz for 15 hours to obtain the ternary co-doped manganese dioxide cathode material, wherein a scanning electron microscope picture is shown in figure 3;
the molar weight of the rutile titanium dioxide is 4mol percent of that of the manganese source; the molar weight of the aluminum sulfate is 6mol percent of that of the manganese source; the molar weight of the nickel sulfate is 2-3 mol% of the molar weight of the manganese source.
Example 4
This example provides a ternary co-doped manganese dioxide material MnTi 0.04 Al 0.06 Ni 0.01 O 2 The preparation method comprises the following steps:
mixing rutile type titanium dioxide, aluminum nitrate, nickel hydroxide and manganese oxalate, and then carrying out first ball milling for 24 hours at the rotation speed of 550rpm and the frequency of 40Hz, wherein the ball-to-material ratio is 5; tabletting the material subjected to the first ball milling under the pressure of 30 tons to obtain flakes with the diameter of 14mm and the thickness of 1.9 mm; calcining the sheet materials at 410 ℃ for 40 hours, then crushing, and performing second ball milling treatment for 13 hours at the rotation speed of 550rpm and the frequency of 40Hz to obtain the ternary codoped manganese dioxide cathode material, wherein a scanning electron microscope image is shown as figure 4;
the molar weight of the rutile titanium dioxide is 4mol percent of that of the manganese source; the molar weight of the aluminum nitrate is 6mol percent of that of the manganese source; the molar weight of the nickel hydroxide is 2-3 mol% of the molar weight of the manganese source.
Example 5
This example provides a method for preparing a ternary co-doped manganese dioxide material, which is different from example 1 in that rutile titanium dioxide is replaced by an equimolar amount of anatase titanium dioxide.
Example 6
This example provides a method for preparing a ternary co-doped manganese dioxide material, which is different from example 1 in that rutile titanium dioxide is replaced by an equimolar amount of titanium sulfate.
Example 7
This example provides a preparation method of a ternary co-doped manganese dioxide material, which is different from example 1 in that the first ball milling is not performed with a tabletting process.
Example 8
This example provides a method for preparing a ternary co-doped manganese dioxide material, which is different from example 1 in that the pressure of the tabletting process is 5 tons.
Example 9
This example provides a method for preparing a ternary codoped manganese dioxide material, which is different from example 1 in that the pressure of the tabletting process is 60 tons.
Example 10
This example provides a method for preparing a ternary codoped manganese dioxide material, which is different from example 1 in that the molar amount of rutile titanium dioxide is 2mol% of the molar amount of manganese carbonate.
Example 11
This example provides a method for preparing a ternary codoped manganese dioxide material, which is different from example 1 in that the molar amount of rutile titanium dioxide is 5mol% of that of manganese carbonate.
Example 12
This example provides a method for preparing a ternary codoped manganese dioxide material, which is different from example 1 in that the molar amount of aluminum nitrate is 4mol% of that of manganese carbonate.
Example 13
This example provides a method for preparing a ternary codoped manganese dioxide material, which is different from example 1 in that the molar amount of aluminum nitrate is 8mol% of that of manganese carbonate.
Example 14
This example provides a preparation method of a ternary codoped manganese dioxide material, which is different from example 1 in that the molar amount of nickel nitrate is 1mol% of that of manganese carbonate.
Example 15
This example provides a preparation method of a ternary codoped manganese dioxide material, which is different from example 1 in that the molar amount of nickel nitrate is 4mol% of that of manganese carbonate.
Comparative example 1
The present comparative example provides an electrolytic manganese dioxide material.
Comparative example 2
The comparative example provides a preparation method of a co-doped manganese dioxide material, which is different from the preparation method of example 1 in that rutile type titanium dioxide is not added.
Comparative example 3
This comparative example provides a method for preparing a co-doped manganese dioxide material, which is different from example 1 in that aluminum nitrate is not added.
Comparative example 4
The comparative example provides a preparation method of a co-doped manganese dioxide material, which is different from example 1 in that nickel nitrate is not added.
Mixing and grinding the manganese dioxide material, super carbon and CMC powder for 20min according to the mass ratio of 8.
Assembling the wafer into CR2032 type button Li-MnO 2 The battery, the method is as follows:
the wafer is used as a positive electrode, a high-purity lithium sheet is used as a negative electrode, and 1mol L of electrolyte is adopted -1 LiClO (r) of 4 The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1. Assembling the components in a glove box under the conditions that the protective atmosphere is high-purity argon and the water oxygen content is less than 0.1ppm, sealing the components by an MSK-110 type manual hydraulic sealing machine, and standing for 2 hours to obtain the CR2032 type button Li-MnO 2 A battery. It was tested and the test results are shown in table 1.
TABLE 1
| Test number | 0.1 Cgram capacity | Capacity exertion rate/%) | Energy density/mWh |
| Example 1 | 251 | 81.49 | 6367.87 |
| Example 2 | 253 | 82.14 | 6418.61 |
| Example 3 | 257 | 83.44 | 6520.09 |
| Example 4 | 261 | 84.74 | 6621.57 |
| Example 5 | 235 | 76.38 | 6002.34 |
| Example 6 | 239 | 78.59 | 6120.57 |
| Example 7 | 232 | 74.46 | 5968.41 |
| Example 8 | 243 | 80.12 | 6245.85 |
| Example 9 | 232 | 75.12 | 6001.82 |
| Example 10 | 233 | 75.65 | 5911.21 |
| Example 11 | 240 | 79.37 | 6157.16 |
| Example 12 | 235 | 75.99 | 5989.74 |
| Example 13 | 244 | 79.70 | 6222.48 |
| Example 14 | 231 | 75.68 | 6032.54 |
| Example 15 | 230 | 74.40 | 5988.63 |
| Comparative example 1 | 223 | 72.40 | 5657.51 |
| Comparative example 2 | 221 | 71.75 | 5606.77 |
| Comparative example 3 | 212 | 68.83 | 5378.44 |
| Comparative example 4 | 210 | 68.18 | 5327.70 |
From table 1, the following conclusions can be drawn:
(1) As can be seen from examples 1-4 and comparative example 1, the invention adopts a synthesis mode of ternary metal co-doped manganese dioxide, improves gram capacity and capacity utilization rate, and increases the platform potential of manganese dioxide, thereby increasing the energy density of the battery.
(2) As is clear from comparison between examples 5 and 6 and example 1, the titanium source in the present invention is rutile type titanium dioxide, and when it is replaced with another titanium source, it is not favorable for doping of the manganese dioxide material, and is not favorable for improvement of the gram volume and the capacity utilization rate.
(3) As is clear from comparison of examples 7 to 9 with example 1, when the tabletting treatment is not performed or the pressure level is not within the preferable range, doping of the manganese dioxide material is not facilitated, and improvement of the gram volume and the capacity utilization rate is not facilitated.
(4) It is understood from the comparison of examples 10 to 15 with example 1 that when the molar amount of the metal element to be doped is out of the preferable range of the present invention, doping of the manganese dioxide material is not facilitated, and improvement of the gram-volume and the capacity utilization rate is not facilitated.
(5) From the comparative examples 2 to 4, it can be seen that the ternary co-doping method adopted in the present invention is not favorable for doping manganese dioxide material and improving gram capacity and capacity utilization rate when doping of one metal element is reduced.
In conclusion, the invention adopts a synthesis mode of ternary metal co-doped manganese dioxide, improves gram capacity and capacity utilization rate, and improves the platform potential of manganese dioxide, thereby increasing the energy density of the battery.
The present invention is described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not meant to be implemented only by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the ternary codoped manganese dioxide material is characterized by comprising the following steps of:
mixing a ternary codoped metal source and a manganese source, calcining, and then crushing to obtain the ternary codoped manganese dioxide cathode material;
the ternary co-doped metal source comprises a titanium source, an aluminum source and a nickel source.
2. The production method according to claim 1, wherein the titanium source includes titanium dioxide;
preferably, the titanium dioxide comprises rutile titanium dioxide;
preferably, the aluminum source comprises any one of aluminum nitrate, aluminum nitrate hydrate, aluminum chloride hydrate, aluminum sulfate or aluminum sulfate hydrate or a combination of at least two of them;
preferably, the nickel source comprises any one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide or nickel hydroxide or a combination of at least two of the nickel nitrate, the nickel acetate, the nickel sulfate, the nickel chloride, the nickel sulfamate and the nickel bromide;
preferably, the manganese source comprises a manganese salt and/or manganese dioxide;
preferably, the manganese salt comprises any one of manganese carbonate, manganese hydroxide or manganese oxalate or a combination of at least two of the same;
preferably, the manganese dioxide is synthesized by a chemical method and/or an electrolytic method.
3. The production method according to claim 1 or 2, wherein the molar amount of the titanium source is 3 to 4mol% of the molar amount of the manganese source;
preferably, the molar amount of the aluminum source is 5 to 7mol% of the molar amount of the manganese source;
preferably, the molar amount of the nickel source is 2 to 3mol% of the molar amount of the manganese source.
4. The method according to any one of claims 1 to 3, wherein the calcining is preceded by ball milling and tabletting;
preferably, the ball-milling ball-material ratio is (4-6) to 1;
preferably, the rotation speed of the ball mill is 500-600 rpm;
preferably, the frequency of the ball milling is 30-50 Hz;
preferably, the ball milling time is 20-25 h;
preferably, the pressure of the compressed tablets is between 10 and 50 tonnes of pressure, preferably between 30 and 50 tonnes of pressure;
preferably, the diameter of the tablet is 10-15 mm;
preferably, the thickness after tabletting is 1.6 to 2mm, preferably 1.8 to 2mm.
5. The method according to any one of claims 1 to 4, wherein the temperature of the calcination is 400 to 420 ℃;
preferably, the calcining time is 24-48 h;
preferably, the calcining further comprises crushing and ball milling;
preferably, the particle size of the ball-milled material is 10-15 μm;
preferably, the time of ball milling after calcination is 10-15 h;
preferably, the frequency of ball milling after calcination is (4-6): 1;
preferably, the rotation speed of the ball mill after calcination is 500-600 rpm;
preferably, the frequency of the ball milling after calcination is 30 to 50Hz.
6. The production method according to any one of claims 1 to 5, characterized by comprising the steps of:
mixing a titanium source, an aluminum source, a nickel source and a manganese source, and then carrying out first ball milling for 20-25 h at the rotating speed of 500-600 rpm and the frequency of 30-50 Hz, wherein the ball-to-material ratio is (4-6) to 1; tabletting the first ball-milled material under 10-50 tons of pressure to obtain a sheet material with the diameter of 10-15 mm and the thickness of 1.6-2 mm; calcining the sheet materials at 400-420 ℃ for 24-48 h, then crushing, and carrying out second ball milling treatment at the rotating speed of 500-600 rpm and the frequency of 30-50 Hz for 10-15 h until the particle size is 10-15 mu m to obtain the ternary co-doped manganese dioxide anode material;
the titanium source is rutile titanium dioxide, and the molar weight of the titanium source is 3-4 mol% of that of the manganese source;
the aluminum source is any one or the combination of at least two of aluminum nitrate, aluminum nitrate hydrate, aluminum chloride hydrate, aluminum sulfate or aluminum sulfate hydrate; the molar weight is 5-7 mol% of the molar weight of the manganese source;
the nickel source comprises any one or the combination of at least two of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide or nickel protoxide; the molar weight is 2-3 mol% of the molar weight of the manganese source;
the manganese source comprises a manganese salt and/or manganese dioxide; the manganese salt comprises any one or a combination of at least two of manganese carbonate, manganese hydroxide or manganese oxalate; the synthesis mode of the manganese dioxide comprises a chemical method and/or an electrolytic method.
7. The ternary codoped manganese dioxide material is obtained according to the preparation method of any one of claims 1 to 6.
8. The ternary codoped manganese dioxide material as claimed in claim 7, wherein the formula of the ternary codoped manganese dioxide cathode material is MnTi x Al y Ni z O 2 Wherein x is in the range of 0.03 to 0.04, y is in the range of 0.05 to 0.07, and z is in the range of 0.01 to 0.03.
9. A positive electrode plate characterized by containing the ternary codoped manganese dioxide material according to claim 7 or 8.
10. A battery comprising the ternary codoped manganese dioxide material according to claim 7 or 8 or the positive electrode sheet according to claim 9.
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