WO2014022989A1 - 掺杂二次电池正极材料及其制备方法 - Google Patents
掺杂二次电池正极材料及其制备方法 Download PDFInfo
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- WO2014022989A1 WO2014022989A1 PCT/CN2012/079827 CN2012079827W WO2014022989A1 WO 2014022989 A1 WO2014022989 A1 WO 2014022989A1 CN 2012079827 W CN2012079827 W CN 2012079827W WO 2014022989 A1 WO2014022989 A1 WO 2014022989A1
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- Prior art keywords
- secondary battery
- dopant
- doped
- powder
- preparation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 title abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002585 base Substances 0.000 claims abstract description 4
- 239000002019 doping agent Substances 0.000 claims description 44
- 239000010406 cathode material Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 14
- -1 alkali metal salt Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 150000001447 alkali salts Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000010902 jet-milling Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000011572 manganese Substances 0.000 description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 6
- 239000011656 manganese carbonate Substances 0.000 description 6
- 235000006748 manganese carbonate Nutrition 0.000 description 6
- 229940093474 manganese carbonate Drugs 0.000 description 6
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 6
- 229940062993 ferrous oxalate Drugs 0.000 description 5
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- DOCYQLFVSIEPAG-UHFFFAOYSA-N [Mn].[Fe].[Li] Chemical compound [Mn].[Fe].[Li] DOCYQLFVSIEPAG-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- ADMWVBXCJSMQLF-UHFFFAOYSA-N C(C)O.[Si] Chemical compound C(C)O.[Si] ADMWVBXCJSMQLF-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 description 1
- GHSTWBLYJDCUQQ-UHFFFAOYSA-N [Ti].[Mn].[Na] Chemical compound [Ti].[Mn].[Na] GHSTWBLYJDCUQQ-UHFFFAOYSA-N 0.000 description 1
- KKCMQBCXXPZGTI-UHFFFAOYSA-N cadmium sodium Chemical compound [Na].[Cd] KKCMQBCXXPZGTI-UHFFFAOYSA-N 0.000 description 1
- SAEBCFDIJRQJQB-UHFFFAOYSA-N carbonic acid;nickel Chemical compound [Ni].OC(O)=O SAEBCFDIJRQJQB-UHFFFAOYSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZYJKUXGOCSWXQO-UHFFFAOYSA-N ethene;silicon Chemical compound [Si].C=C ZYJKUXGOCSWXQO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Definitions
- the present invention relates to the field of battery cathode materials, and in particular to a doped secondary battery cathode material and a preparation method thereof.
- positive electrode materials commonly used in secondary batteries are: lead, nickel hydrogen, lithium cobaltate, lithium nickel cobaltate, lithium manganate, ternary and lithium iron phosphate, and the like.
- Lithium cobaltate and lithium nickel cobaltate are oxides of a hexagonal layered rock salt structure. The electrons in lithium ions move in the octahedral gap formed by 0-Co-0, which has high conductivity and lithium ion deintercalation. / Embedding reversibility.
- Lithium manganate is an oxide of the three-dimensional structure of spinel.
- the electrons in lithium ions move in the octahedral cubic channel composed of 0-Mn-0, and also have high conductivity and lithium ion deintercalation/embedded reversibility. They are all positive materials for a large number of applications in the current lithium battery industry.
- metallic cobalt is one of the scarcest elements on the earth and is radioactive. Its oxide reacts violently with the electrolyte when the battery is overcharged and overdischarged, releasing a large amount of heat and causing the battery to ignite until it explodes. Therefore, lithium cobaltate and lithium nickel cobaltate are expensive to manufacture and have poor safety.
- lithium manganate is cheaper and safer, it has a small capacitance and a poor cycle life under high temperature conditions (above 55 °C). Even after doping and surface chemical treatment, the cycle life of lithium manganate batteries cannot meet the actual requirements. Therefore, the lithium battery industry, especially high-power lithium batteries, urgently needs a cathode material that is low in cost, environmentally friendly, large in capacity, and safe.
- Lithium iron phosphate polycrystalline LiFeP0 4 Lithium iron phosphate polycrystalline LiFeP0 4 .
- the lithium ion electrons in the crystal are free to move in the Fe0 6 octahedron and P0 4 tetrahedral structures, and have deintercalation/embedded reversibility of lithium ions.
- the theoretical discharge capacity of the lithium iron phosphate polycrystal can reach 170 mAh/g.
- lithium iron phosphate Due to the abundant reserves of lithium and iron, the production cost of lithium iron phosphate is low. The article predicts that lithium iron phosphate materials are cheap and environmentally friendly. Features such as high performance and safety, which may have broad application prospects in the battery industry.
- lithium iron phosphate has a very low electrical conductivity (10 - 9 S/cm) at room temperature, and the actual discharge capacity of lithium iron phosphate is only a theoretical value under normal discharge current (lC ⁇ mA/cm 2 ). 10% of 170mAh/g). Therefore, its application in the battery is limited.
- a recent article Suag-Yoon Chang, Jason T.
- the present invention provides a doped secondary battery positive electrode material, which is doped with a secondary metal salt as a base material, doped with conductive doping ions and pressurized doping ions,
- the chemical formula is:
- A is Li + , Na + or K .
- the lanthanum is Fe 2+ , Mn 2+ , Cu 2+ , Zn 2+ , V 2+ , Sn 2+ , W 2+ , Mo 2+ , Ni 2+ , Co 2+ , Cr 2+ , Ti One of 2+ or Pb 2+ or any combination of two or more thereof. More preferably, B is Fe 2+ .
- F is Si0 4 4 -, Ti0 4 4 - or Ge0 4 4 -.
- the doped secondary battery positive electrode material has a particle diameter of 40 to 80 nm.
- the invention provides a preparation method of the above-mentioned doped secondary battery positive electrode material, comprising the following steps:
- step 2) After the powder obtained in the step 1) is granulated, it is sintered at 200 to 300 ° C for 2 to 3 hours under an inert gas atmosphere;
- step 2) cooling the product obtained in step 2) to room temperature, adding a carbon source, crushing into a powder, and mixing uniformly;
- step 4) After the powder obtained in the step 3) is granulated, the temperature is raised to 500 to 800 ° C in an inert gas atmosphere, and the temperature is sintered for 8 to 15 hours;
- step 5 is cooled to room temperature and pulverized.
- the alkali metal salt is A(Ac), A 2 C0 3 or A 2 C 2 0 4 .
- the salt of the positive divalent metal is B(Ac) 2 , BC0 3 or BC 2 0 4 .
- the conductive dopant is a compound of Mg 2+ , Ca 2+ , Sr 2+ , Nd 2+ , Sm 2+ or Eu 2+ or a mixture of two or more thereof.
- the pressurized dopant is a compound of Ni 2+ , Mn 2+ , Co 2+ , Cu 2+ or Zn 2+ or a mixture of two or more thereof.
- the anionic starting compound is Si(OC 2 3 ⁇ 4 ) 4 , Ti(OC 2 3 ⁇ 4 ) 4 , Ge(OC 2 3 ⁇ 4 ) 4 , silicic acid, titanic acid, citric acid, SiO 2 , Ti 0 2 , or Ge 0 2 .
- the carbon source is glucose or graphene.
- the mixing method of the raw materials in the step 1) is:
- the mixing method of the raw materials in step 1) is:
- alkali metal salt A (Ac) or A 2 C0 3 or A 2 C 2 0 4
- salt of divalent metal B (Ac) 2 or BC0 3 or BC 2 0 4
- conductive dopant increase
- the pressure dopant and the anion starting compound are placed in a reflux system equipped with water and ethanol, stirred at 80 ° C for 20 to 24 hours, and dried for use.
- the doped nano-scale secondary battery cathode material provided by the invention adds a positive ion having a small atomic weight and a high polarizability as a conductive doping ion, and the conductivity of the positive electrode material is from 3 ⁇ 10- 9 to 10- 15
- the S/cm is increased to 1 X 10- 2 S/cm, which is increased by 10 7 ⁇ 10 13 times.
- the pressurized doping ions with wide oxidation-reduction potential window are added to change the chemical potential energy of the crystal structure of the positive electrode material, and the discharge voltage is increased.
- the invention also provides a preparation method of the above-mentioned doped secondary battery positive electrode material, which has the characteristics of low production cost, simple operation method, no pollution in production and high yield (> 98%).
- FIG. 1 A positive electrode material of a nano-sized doped secondary battery prepared in Example 1 ( ⁇ 6. 5 ⁇ 11..45 ⁇ 0 4 /0 ) . 5 ) Scanning electron micrograph, magnification: 80,000 times; scale bar: 1.0 ⁇ .
- FIG 1 B Example 1 Preparation of nano-doped secondary battery positive electrode material (Li 2 (Fe .. 55 Mn .. 45) Si0 4 / C ... 5)
- FIG TEM (b) dimensions: 100nm.
- the material has a particle diameter of 40 to 80 nm.
- Fig. 2 Charging and discharging characteristics of a lithium-ion battery made of a nano-sized doped secondary battery prepared in Example 1 (Li 2 (Fe Q . 55 Mn Q .4 5 ) Si04/C Q . Q5 ) Graph.
- Figure 3 Nanoscale doped secondary battery cathode material prepared in Example 1
- the invention provides a doped secondary battery cathode material with an alkali metal salt as a base material, a conductive dopant and a pressurized doping ion, and the chemical formula is:
- a 2 [B m (D x E 1-x ) 1-m ]F crystal belongs to orthorhombic olivine-type structure, and electrons are 0-Si— 0 (or 0—Ti—0, 0—Ge— 0 )
- the movement of the formed tetrahedral layer gap has a high reversibility of alkali metal ion deintercalation/embedding.
- Carbon is only filled in the gap of A ⁇ B DxE ⁇ JF crystal, and coated on the surface of A 2 [B m (D x E 1 ⁇ cm ]F crystal body to improve its electrical conductivity. It has an excellent performance and can be exchanged. Two electrons, so its theoretical capacitance is up to 333mAh/g 0
- the first step is to take 2 moles of lithium acetate (LiAc); 0.55 moles of ferrous oxalate; pressurized dopant: 0.45 moles of manganese carbonate, and 1 mole of silicon ethoxide (Si(OC 2 3 ⁇ 4 ) 4 Mixing with water and ethanol in a reflux system for 20 hours, the temperature in the system is controlled at 80 °C; and then drying at 120 ° C;
- the powder prepared in the first step is granulated and placed in an alumina ceramic crucible for nitrogen.
- a gas (or argon) furnace the temperature is raised to 200 to 300 ° C, and the temperature is sintered for 2 hours. (At this temperature, C, H, and 0 are emitted as CO, C0 2 , 3 ⁇ 40, etc., the same below.);
- the mixture is taken out, and 0.05 mole of graphene is added; the powder is ground into a powder and mixed uniformly;
- the temperature is raised to 500-650 ° C in a nitrogen (or argon) furnace, and the temperature is sintered for 8 to 15 hours, and naturally falls to room temperature;
- the crystal agglomerate is crushed into a powder form
- the powder prepared in the fifth step is crushed and classified on a superfine jet mill to prepare a nano-scale doped secondary battery cathode material, and the particle diameter is 40 to 80 nm by SEM and TEM (see FIG. 1A and Figure 1B).
- the positive electrode material of the doped secondary battery prepared in this embodiment was detected and analyzed by XRD (as shown in FIG. 3), and its structural formula is: Li 2 (Fe.. 55 Mn.. 45 ) SiO 4 /C 0 . 05 .
- the ordinary lithium iron manganese silicate positive electrode material has a conductivity of 3 x 10 _ 15 S/cm, and the room temperature discharge average voltage is 3.8 V; and as shown in FIG. 2, the nano-sized doped secondary battery provided in this embodiment
- the room temperature conductivity and room temperature discharge voltage of the positive electrode material were 1.30 x 10_ 2 S/cm and 4.2 V, respectively, which were increased by 10 13 times and 10.53%, respectively.
- the actual discharge capacity is > 260 mAh/g (the theoretical discharge capacity is 333 mAh/g).
- LiAc lithium acetate
- ferrous oxalate 0.05 moles of ferrous oxalate
- conductive dopant 0.095 moles of magnesium oxide
- pressurized dopant 0.38 moles of manganese carbonate, 0.475 moles of cobalt carbonate, and 1 mole Ethylene silicon Si(OC 2 3 ⁇ 4 ) 4 was placed in a reflux system equipped with water and ethanol for 20 hours, and the temperature in the system was controlled at 80 °C; then dried at 120 ° C;
- the powder prepared in the first step is granulated, placed in an alumina ceramic crucible, heated to 200 to 300 ° C in a nitrogen (or argon) furnace, and sintered at a constant temperature for 2 hours;
- the third step is taken out after cooling to room temperature, and 0.01 mol of glucose is added; the ball is ground into a powder and mixed uniformly;
- the temperature is raised to 500-650 ° C in a nitrogen (or argon) furnace, and the temperature is sintered for 8 to 15 hours, and naturally falls to room temperature;
- the crystal agglomerate is crushed into a powder form;
- the powder prepared in the fifth step is crushed and classified on a superfine jet mill to prepare a nano-scale doped secondary battery positive electrode material, and the particle diameter is 40 to 80 nm.
- the positive electrode material of the doped secondary battery prepared in this embodiment is detected and analyzed by XRD, and its structural formula is: Li Feo.o ⁇ Mgo.iMno ⁇ Coo. ⁇ o. ⁇ SiC Co.o ⁇
- the ordinary lithium iron manganese silicate positive electrode material has a conductivity of 3 x 10 _ 15 S/cm, and the room temperature discharge average voltage is 3.8 V; and the room temperature conductivity of the nano-sized doped secondary battery positive electrode material provided in this embodiment
- the discharge voltages at room temperature were 1.30 x lO_ 2 S/cm and 4.0 V, respectively, which were increased by 10 13 times and 5.3%, respectively.
- the actual discharge capacity is > 260 mAh/g (the theoretical discharge capacity is 333 mAh/g).
- the first step 2 moles of lithium acetate (LiAc. 23 ⁇ 40); 0.1 moles of ferrous oxalate; conductive dopant: 0.27 moles of magnesium oxide; pressurized dopant: 0.18 moles of manganese carbonate, 0.45 moles of cobalt carbonate, and 1 mole of solid ethanol silicon Si(OC 2 3 ⁇ 4 ) 4 is placed in a ZrO ball mill, ball milled, stirred and mixed for the second step, and the powder prepared in the first step is granulated, and then placed in an alumina ceramic crucible, under nitrogen. (or argon) furnace to raise the temperature to 200 ⁇ 300 ° C, constant temperature sintering 1.5 ⁇ 2.5 hours;
- the third step after cooling to room temperature, take out, ball mill into powder, add 0.01 mole of graphene; ball mill and stir evenly;
- the temperature is further raised to 500 to 650 ° C in a nitrogen (or argon) furnace, and the temperature is sintered for 8 to 15 hours, and the temperature is naturally lowered to room temperature;
- the crystal agglomerate is crushed into a powder form
- the powder prepared in the fifth step is crushed and classified on a superfine jet mill to prepare a nano-scale doped secondary battery positive electrode material, and the powder particles have a diameter of 40 to 80 nm.
- the positive electrode material of the doped secondary battery prepared in this embodiment is detected and analyzed by XRD, and its structural formula is:
- the conductivity of the common lithium iron manganese silicate cathode material is 3 X 10 _ 15 S/cm, and the room temperature discharge average voltage is 3.8 V; and the room temperature conductivity of the nano-scale doped secondary battery cathode material provided in this embodiment
- the discharge voltages at room temperature were 1.30 x lO_ 2 S/cm and 4.1 V, respectively, which were increased by 10 13 times and 7.9%, respectively.
- the actual discharge capacity is > 260 mA / g (the theoretical discharge capacity is 333 mAh / g).
- the first step 1 mole of lithium carbonate (Li 2 C0 3 ); 0.4 mole of ferrous oxalate; conductive dopant: 0.12 moles of magnesium oxide; pressurized dopant: 0.24 moles of manganese carbonate, 0.24 moles of basic carbonic acid Nickel, and 1 mole of nano Ti0 2 , placed in a ZrO ball mill, ball milled, stirred and mixed for 2 to 3 hours, crushed the second step, the first step of the powder is granulated, and then placed in an alumina ceramic crucible, Heating in a nitrogen (or argon) furnace to 200 ⁇ 300 ° C, and sintering at a constant temperature for 2 to 3 hours;
- the temperature is further raised to 500 to 650 ° C in a nitrogen (or argon) furnace, and the temperature is sintered for 8 to 15 hours, and the temperature is naturally lowered to room temperature;
- the crystal agglomerate is crushed into a powder form
- the powder prepared in the fifth step is crushed and classified on a superfine jet mill to prepare a nano-scale doped secondary battery positive electrode material, and the particle diameter is 40 to 80 nm.
- the positive electrode material of the doped secondary battery prepared in this embodiment was detected and analyzed by XRD, and its structural formula was: Li 2 [Fe. .4 (Mg.. 2 Mn.. 4Ni..4). . 6 ]TiO 4 /C 0 . 0 4
- the ordinary lithium iron manganese titanate positive electrode material has a conductivity of 3 X 10 _ 13 S/cm, and the room temperature discharge average voltage is 3.7 V; and the room temperature conductivity of the nano-sized doped secondary battery cathode material provided in this embodiment
- the discharge voltages at room temperature were 1.30 x 10_ 2 S/cm and 4.2 V, respectively, which were increased by 10 11 times and 13.51%, respectively.
- the actual discharge capacity is > 260 mAh/g (the theoretical discharge capacity is 328 mAh/g).
- the first step 1 mol of sodium carbonate (Na 2 CO 3 ); 0.95 mol of zinc oxalate; conductive dopant: 0.01 mol of calcium oxide; pressurized dopant: 0.02 mol of manganese carbonate, 0.02 mol of basic nickel carbonate , and 1 mol of nano-SiO 2 , put into a ZrO ball mill, ball mill, stir and mix for 2 to 3 hours, crush the second step, granule the powder prepared in the first step, and then put it into the alumina ceramic crucible, Heating in a nitrogen (or argon) furnace to 200 ⁇ 300 ° C, and sintering at a constant temperature for 2 to 3 hours;
- the third step after cooling to room temperature, take out, add 0.03 mole of graphene; ball mill into powder, stir evenly;
- the fourth step after the powder obtained in the third step is granulated, the temperature is further increased to 650 to 800 ° C in a nitrogen (or argon) furnace, and the temperature is sintered for 8 to 15 hours, and the temperature is naturally lowered to room temperature;
- the crystal agglomerate is crushed into a powder form
- the powder prepared in the fifth step is crushed and classified on a superfine jet mill to prepare a nano-scale doped secondary battery positive electrode material, and the particle diameter is 40 to 80 nm.
- the positive electrode material of the doped secondary battery prepared in this embodiment is detected and analyzed by XRD, and its structural formula is: Na 2 [Zn 0 . 95 (Ca 0 . 2 Mn 0 .4Ni 0 .4) 0 . 05 ] SiO 4 / C 0 . 03 .
- the conductivity of the ordinary sodium cadmium silicate positive electrode material is determined to be 3 x lO- u S/cm, and the average discharge voltage at room temperature is 2.7 V; and the room temperature conductivity of the positive electrode material of the nano-sized doped secondary battery provided in this embodiment
- the discharge voltages at room temperature were 1.30 x 10_ 2 S/cm and 4.0 V, respectively, which were increased by 10 9 and 48%, respectively.
- the actual discharge capacity is > 250 mAh/g.
- the first step 1 mole of potassium carbonate (K 2 C0 3 ); 0.5 mole of ferrous oxalate; conductive dopant: 0.05 moles of calcium oxide, 0.05 moles of magnesium oxide; pressurized dopant: 0.2 moles of manganese carbonate, 0.2 mole of basic nickel carbonate, and 1 mole of nano-SiO 2 , put into a ZrO ball mill, ball mill, stir and mix 2 ⁇ 3.
- the first step of the powder is granulated, and then placed in an alumina ceramic crucible. In the nitrogen (or argon) furnace, the temperature is raised to 200 ⁇ 300 ° C, and the temperature is sintered for 2 to 3 hours;
- the temperature is further increased to 650 to 800 ° C in a nitrogen (or argon) furnace, and the temperature is sintered for 8 to 15 hours to form a doped nano sodium titanium manganese silicate. Salt crystals, naturally cooled to room temperature;
- the crystal agglomerate is crushed into a powder form
- the powder prepared in the fifth step is crushed and classified on a superfine jet mill to prepare a nano-scale doped secondary battery positive electrode material, and the particle diameter is 40 to 80 nm.
- the positive electrode material of the doped secondary battery prepared in this embodiment is detected and analyzed by XRD, and its structural formula is: K ⁇ Feo.s Cao.iMgfuMn ⁇ Nio ⁇ o. ⁇ SiC Co.o
- the conductivity of ordinary potassium manganese silicate cathode material is 3 X 10- u S/cm, room temperature discharge The average voltage is 2.7V; and the room temperature conductivity and the room temperature discharge voltage of the nano-sized doped secondary battery cathode material provided in this embodiment are 1.30 x 10_ 2 S/cm and 4.0 V, respectively, which are increased by 109 times and 48, respectively. %.
- the actual discharge capacity is > 245 mAh/g.
- the nano-doped secondary battery positive electrode materials provided in Embodiments 1 to 6 of the present invention can be rapidly charged at a rate of 0.1 C 10 C, rapidly discharged at a rate of 30 C, and have a charging life of more than 4000 times, wherein the actual discharge capacities of Examples 1 to 4 More than 260mAh / g.
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Abstract
提供一种掺杂二次电池正极材料及其制备方法。该掺杂二次电池正极材料以碱金属盐为基材,掺有导电掺杂离子和增压掺杂离子,其化学通式为:A2[Bm(DxE1-x)1-m]F/Cy,其中A为碱金属离子中的一种;B为正二价金属离子中的一种或其两种以上任意组合;C为碳;D为导电掺杂离子,其为Mg2+、Ca2+、Sr2+、Nd2+、Sm2+或Eu2+中的一种或其两种以上任意组合;E为增压掺杂离子,其为Mn2+、Ni2+、Co2+、Cu2+、Zn2+中的一种或其两种以上任意组合;F为负4价阴离子;x=0~0.3,m=0.05~0.95,y=0.01~0.06。该掺杂二次电池正极材料通过液相或固相反应制得:所有原料用液相或固相混合均匀——碎成粉末——压粒——隋性氛围200~300°C恒温烧结2~3小时——冷却——加碳源并碎成粉体——压粒——隋性氛围500-700°C恒温烧结8~15小时——冷却——碎成粉体——气流粉碎、分级。本方法生产成本低、操作简单、环保、成品率高。该掺杂二次电池正极材料导电率优于10-2S/cm,实际放电容量>260mAh/g(其理论放电容量为333mAh/g),可快速大功率充放电,具有低价、高能、安全、环保等特征,适用于小型固体、聚合物、胶体和液体二次电池,尤其适用于大功率动力电池。
Description
掺杂二次电池正极材料及其制备方法
技术领域 本发明属于电池正极材料领域, 具体涉及一种掺杂二次电池正极材料 及其制备方法。 背景技术 目前, 二次电池中常用的正极材料有: 铅、 镍氢、 钴酸锂、 镍钴酸锂、 锰酸锂、 三元和磷酸铁锂等。 钴酸锂和镍钴酸锂是六方晶系层状岩盐结构 的氧化物, 锂离子中的电子在 0— Co— 0构成的八面体层间隙中移动, 具 有较高的导电性能和锂离子脱嵌 /嵌入的可逆性。 锰酸锂是尖晶石三维结构 的氧化物, 锂离子中的电子在 0— Mn— 0构成的八面体立方通道中移动, 也具有较高的导电性能和锂离子脱嵌 /嵌入可逆性。 它们都是当前锂电池工 业中大量应用的正极材料。 但金属钴是地球上稀缺的元素之一, 且具有放 射性, 其氧化物在电池过充和过放时会与电解液发生剧烈反应, 放出大量 热量而致使电池起火直至爆炸。 因此, 钴酸锂和镍钴酸锂的制造成本高, 安全性差。 铅、 镍、 钴又是严重的污染和致癌物质。 锰酸锂虽然较便宜和 安全, 可是电容量小, 而且在高温条件下 (55 °C以上) 的循环使用寿命差。 即使经过掺杂和表面化学处理, 锰酸锂电池的循环使用寿命仍然无法满足 实际要求。 因此, 锂电池工业, 特别是大功率锂电池急需一种成本低廉、 环保、 容量大和安全的正极材料。
为此, 美国德州大学教授 J. B .Goodenough 等 (A. K. Padhi, K. S.
Najundaswamy , C .Masgueslier , S. Okada and J. B. Goodenough , J. Eletrochem. Soc. 144, 1609—1613 ( 1997 ) )于 1997年在美国电化学杂志 上发表文章, 公开了一种新的嵌锂化合物: 锂铁磷酸盐多晶体 LiFeP04。 该 晶体中的锂离子电子在 Fe06八面体和 P04四面体结构中自由移动, 具有锂 离子的脱嵌 /嵌入可逆性。 当 1摩尔的锂离子从结构中脱嵌出来时, 锂铁磷 酸盐多晶体的理论放电容量可达 170mAh/g。 由于锂、 铁储量丰富, 锂铁磷 酸盐的生产成本低廉。 该文预测, 由于锂铁磷酸盐材料具有价廉、 环保、
高性能和安全等特征, 其在电池工业中可能具有广阔的应用前景。 但是, 锂铁磷酸盐在室温下电导率极低( 10-9S/cm ),在正常放电电流( lC^mA/cm2 ) 条件下, 锂铁磷酸盐的实际放电容量仅为理论值(170mAh/g ) 的 10%。 因 此, 限制了其在电池中的应用。 为了提高锂铁磷酸盐的电导率, 近期有文 章报道 ( Suag-Yoon Chang, Jason T. Bloking and Yetming Chiang, Nature, October 123-128(2002) ), 在其结构中加入微量添加剂, 如 Mg、 Ti、 Nb和 Zr等, 室温下的电导率有了较大提高。 但是, 该文中提到的添加剂的加入 方法复杂, 微量元素的价格高, 不适合大规模工业生产。 此外, 锂铁磷酸 盐的室温导电空间较大, 但其放电电压较低, 从而影响了该材料的能量密 度。
如何制备出更经济, 更环保, 更安全的动力电池, 满足人类幸福生活 的需要, 就要研制出电压和电容量更高的正极材料。 发明内容 为了解决上述技术问题, 本发明提供一种掺杂二次电池正极材料, 掺 杂二次电池正极材料以碱金属盐为基材, 掺有导电掺杂离子和增压掺杂离 子, 其化学通式为:
A2[Bm(DxE1-x)1-m]F/Cy
其中, A为碱金属离子中的一种; B为正二价金属离子中的一种或其两 种以上任意组合; C为碳; D为导电掺杂离子, 其为 Mg2+、 Ca2+ 、 Sr2+、 Nd2+、 Sm2+或 Eu2+中的一种或其两种以上任意组合; E为增压掺杂离子, 其 为 Mn2+、 Ni2+、 Co2+ 、 Cu2+或 Zn2+中的一种或其两种以上任意组合; F为 负 4价阴离子;
x = 0〜0.3 , m = 0.05〜0.95, y =0.01〜0.06。
优选地, A为 Li+、 Na+或 K 。
优选地, Β为 Fe2+、 Mn2+、 Cu2+、 Zn2+、 V2+、 Sn2+、 W2+、 Mo2+、 Ni2+、 Co2+、 Cr2+、 Ti2+或 Pb2+中的一种或其两种以上任意组合。 更优选地, B为 Fe2+。
优选地, F为 Si04 4—、 Ti04 4—或 Ge04 4—。
优选地, 掺杂二次电池正极材料的颗粒直径为 40〜80 nm。
本发明提供上述的掺杂二次电池正极材料的制备方法, 包括如下步骤:
1 )计算所需原料量, 取原料: 碱金属盐, 正二价金属的盐, 导电掺杂 剂, 增压掺杂剂和阴离子原料化合物, 混合均匀;
2 )将步骤 1 )得到的粉体压粒后, 在惰性气体环境下, 在 200〜300°C 恒温烧结 2〜3小时;
3 )将步骤 2 )得到的产物冷却至室温, 加入碳源, 碎成粉体、 混合均 匀;
4 )将步骤 3 )所得粉体压粒后,在惰性气体环境下,升温到 500〜800°C , 恒温烧结 8〜15小时;
5 )将步骤 5所得冷却至室温, 粉碎, 即得。
优选地, 步骤 1 )中, 各原料的摩尔比为: 碱金属盐中碱金属离子: [二 价金属的盐中金属离子 + (导电掺杂剂 +增压掺杂剂)]: 阴离子原料化合物: 碳源中碳元素 = 2:1:1 :0.01〜0.06, 其中, 二价金属的盐中金属离子: (导电掺 杂剂 +增压掺杂剂) =0.05〜0.95:0.95〜0.05, 导电掺杂剂: 增压掺杂剂的摩尔 比为 0〜0.3:0.7〜1。
优选地, 碱金属盐为 A(Ac)、 A2C03或 A2C204。
优选地, 正二价金属的盐为 B(Ac)2 、 BC03或 BC204。
优选地, 导电掺杂剂为 Mg2+、 Ca2+ 、 Sr2+ 、 Nd2+、 Sm2+或 Eu2+的化合 物或其两种以上任意混合物。
优选地, 增压掺杂剂为 Ni2+、 Mn2+、 Co2+ 、 Cu2+或 Zn2+的化合物或其 两种以上任意混合物。
优选地, 阴离子原料化合物为 Si(OC2¾)4、 Ti(OC2¾)4、 Ge(OC2¾)4、 硅酸、 钛酸、 锗酸、 Si02、 Ti02、 或 Ge02。
优选地, 碳源为葡萄糖或石墨烯。
作为一优选方案, 步骤 1 ) 中原料的混合方法为:
取原料: 碱金属盐: A(Ac)或 A2C03或 A2C204, 二价金属的盐: B(Ac)2 或 BC03或 BC204, 导电掺杂剂, 增压掺杂剂和阴离子原料化合物, 在球磨 机中碎成粉体。
作为另一优选方案, 步骤 1 ) 中原料的混合方法为:
取原料: 碱金属盐: A(Ac)或 A2C03或 A2C204, 二价金属的盐: B(Ac)2 或 BC03或 BC204, 导电掺杂剂, 增压掺杂剂和阴离子原料化合物, 放入配 有水和乙醇的回流系统中, 80°C搅拌 20〜24小时, 烘干备用。
本发明提供的掺杂纳米级二次电池正极材料, 添加了原子量较小而极 化率极高的正离子作为导电掺杂离子, 将正极材料的电导率从 3 χ 10-9 ~ 10-15S/cm提高到 1 X 10-2S/cm, 提高了 107 ~ 1013倍; 同时添加氧化还原电 位窗口较宽的增压掺杂离子改变正极材料晶体结构的化学势能, 提高了放 电电压(即工作电压), 使其提高了 10.53%; 另外, 该材料的实际放电容量 超过 260mAh/g; 还可以高倍率充、 放电, 可实现一分钟快速充电, 充电寿 命超过 4000次。 该材料不仅可以应用于小容量的二次电池, 而且应用在 100安时以上的大容量、 大功率二次电池中更有价值。 本发明还提供了上述 掺杂二次电池正极材料的制备方法, 该方法具有生产成本低、 操作方法简 单、 生产中无污染和成品率高 ( > 98% ) 的特点。
本方法生产成本低、 操作简单、 环保、 成品率高。 通过本液相或固相 反应制成的掺杂二次电池正极材料,其导电率优于 10-2S/cm, 实际放电容量 > 260mAh/g (其理论放电容量为 333mAh/g), 可快速大功率充放电, 具有低 价、 高能、 安全、 环保等特征, 适用于小型固体、 聚合物、 胶体和液体二 次电池, 尤其适用于大功率动力电池。 附图说明 图 l a: 实施例 1 制备的纳米级掺杂二次电池正极材料 ( ^6。.5^11。.45^04/0).。5)的扫描电镜图, 放大倍数: 80,000 倍; 比例尺: 1.0μηι。
图 1 b: 实施例 1 制备的纳米级掺杂二次电池正极材料 (Li2(Fe。.55Mn。.45)Si04/C。.。5)的透射电镜图 (b ), 比例尺: 100nm。 该材料的 颗粒直径为 40〜80nm。
图 2: 实施例 1 制备的纳米级掺杂二次电池正极材料 (Li2(FeQ.55MnQ.45)Si04/CQ.Q5)制成的扣式锂电池的充、 放电特征曲线图。
图 3: 实施例 1 制备的纳米级掺杂二次电池正极材料
(Li2(Fe。.55Mn。.45)Si04/C。.。5)的 x射线衍射图。 具体实施方式 下面结合附图和具体实施例对本发明作进一步说明, 以使本领域的技 术人员可以更好的理解本发明并能予以实施, 但所举实施例不作为对本发 明的限定。
本发明提供掺杂二次电池正极材料以碱金属盐为基材, 掺有导电掺杂剂 和增压掺杂离子, 其化学通式为:
A2[Bm(DxE1-x)1-m]F/Cy
其中, A为碱金属离子中的一种; B为正二价金属离子中的一种或其 两种以上任意组合; C为碳; D为导电掺杂剂, 其为 Mg2+、 Ca2+ 、 Sr2+、 Nd2+、 Sm2+或 Eu2+中的一种或其两种以上任意组合; E为增压掺杂剂, 其为 Mn2+、 Ni2+、 Co2+ 、 Cu2+或 Zn2+中的一种或其两种以上任意组合; F为负 4 价阴离子;
x = 0〜0.3 , m = 0.05〜0.95, y =0.01〜0.06。
A2[Bm(DxE1-x)1-m]F 结晶体属于正交晶系橄榄石型结构, 电子在 0— Si— 0 (或 0— Ti一 0、 0— Ge— 0 )构成的四面体层间隙中移动, 具有 较高的碱金属离子脱嵌 /嵌入的可逆性。 碳仅充填于 A^B DxE^ JF结晶 体间隙中, 和包覆于 A2[Bm(DxE1→c m]F结晶体的表面, 改善其导电性能。 其有一个优异性能, 就是可以交换两个电子, 所以其理论电容量高达 333mAh/g0
实验中的较佳实施例如下:
实施例 1
本实施例掺杂二次电池正极材料的制备方法如下:
第一步,取 2摩尔醋酸锂(LiAc ); 0. 55摩尔乙二酸亚铁;增压掺杂剂: 0.45摩尔碳酸锰, 和 1摩尔乙醇硅(Si(OC2¾)4放入配有水和乙醇的回流系 统中搅拌混合 20小时, 系统中温度控制在 80度; 再在 120°C下烘干;
第二步, 将第一步制好的粉体压粒后, 放入氧化铝陶瓷坩锅中, 于氮
气 (或氩气)炉中升温至 200〜300°C , 恒温烧结 2小时(此温度下烧结中, C、 H、 0以 CO,C02, ¾0等气体排放, 以下相同。);
第三步, 冷却至室温后取出, 加入 0.05摩尔石墨烯; 球磨成粉体、 混 合均匀;
第四步, 将第三步得到的粉体压粒后, 在氮气 (或氩气) 炉中升温至 500-650 °C , 恒温烧结 8〜15小时, 自然降至室温;
第五步, 将结晶团块压碎至粉末状;
第六步, 将第五步制备的粉末在超微气流粉碎机上进行破碎和分级, 制成纳米级掺杂二次电池正极材料, 经 SEM 和 TEM 测定颗粒直径为 40〜80nm (见图 1A和图 1B )。
本实施例制得的掺杂二次电池正极材料经 XRD检测及分析(如图 3所 示), 其结构式为: Li2(Fe。.55Mn。.45)SiO4/C0.05。
经测定, 普通锂铁锰硅酸盐正极材料电导率为 3 x 10_15S/cm, 室温放电 平均电压为 3.8V; 而如图 2所示, 本实施例提供的纳米级掺杂二次电池正 极材料的室温电导率和室温放电电压分别为 1.30 x 10_2S/cm和 4.2V, 分别 提高了 1013倍和 10.53%。 实际放电容量 > 260mAh/g (其理论放电容量为 333mAh/g )。
实施例 2
本实施例掺杂二次电池正极材料的制备方法如下:
第一步, 取 2摩尔醋酸锂(LiAc ); 0.05摩尔乙二酸亚铁; 导电掺杂剂: 0.095摩尔氧化镁; 增压掺杂剂: 0.38摩尔碳酸锰、 0.475摩尔碳酸钴, 和 1 摩尔乙醇硅 Si(OC2¾)4放入配有水和乙醇的回流系统中搅拌混合 20小时, 系统中温度控制在 80度; 再在 120°C下烘干;
第二步, 将第一步制好的粉体压粒后, 放入氧化铝陶瓷坩锅中, 于氮 气 (或氩气)炉中升温至 200〜300°C , 恒温烧结 2小时;
第三步, 冷却至室温后取出, 加入 0.01摩尔葡萄糖; 球磨成粉体、 混 合均匀;
第四步, 将第三步得到的粉体压粒后, 在氮气 (或氩气) 炉中升温至 500-650 °C , 恒温烧结 8〜15小时, 自然降至室温;
第五步, 将结晶团块压碎至粉末状;
第六步, 将第五步制备的粉末在超微气流粉碎机上进行破碎和分级, 制成纳米级掺杂二次电池正极材料, 颗粒直径为 40〜80nm。
本实施例制得的掺杂二次电池正极材料经 XRD检测及分析,其结构式 为: Li Feo.o^Mgo.iMno^Coo.^o.^SiC Co.o^
经测定, 普通锂铁锰硅酸盐正极材料电导率为 3 x 10_15S/cm, 室温放电 平均电压为 3.8V; 而本实施例提供的纳米级掺杂二次电池正极材料的室温 电导率和室温放电电压分别为 1.30 x lO_2S/cm和 4.0V, 分别提高了 1013倍 和 5.3%。 实际放电容量 > 260mAh/g (其理论放电容量为 333mAh/g )。
实施例 3
第一步, 取 2摩尔 醋酸锂 (LiAc.2¾0 ); 0.1摩尔乙二酸亚铁; 导电 掺杂剂: 0.27摩尔氧化镁; 增压掺杂剂: 0.18摩尔碳酸锰、 0.45摩尔碳酸 钴, 和 1摩尔固体乙醇硅 Si(OC2¾)4放入 ZrO球磨机中, 球磨、 搅拌混合 第二步, 将第一步制好的粉体压粒后, 放入氧化铝陶瓷坩锅中, 于氮 气 (或氩气)炉中升温至 200〜300°C , 恒温烧结 1.5〜2.5小时;
第三步, 冷却至室温后取出, 球磨成粉体、 加入 0.01摩尔石墨烯; 球 磨并搅拌均匀;
第四步, 将第三步得到的粉体压粒后, 在氮气 (或氩气) 炉中继续升 温至 500〜650°C , 恒温烧结 8〜15小时, 自然降温至室温;
第五步, 将结晶团块压碎至粉末状;
第六步, 将第五步制备的粉末在超微气流粉碎机上进行破碎和分级, 制成纳米级掺杂二次电池正极材料, 粉体颗粒直径为 40〜80nm。
经测定, 普通锂铁锰硅酸盐正极材料电导率为 3 X 10_15S/cm, 室温放 电平均电压为 3.8V; 而本实施例提供的纳米级掺杂二次电池正极材料的室 温电导率和室温放电电压分别为 1.30 x lO_2S/cm和 4.1V, 分别提高了 1013 倍和 7.9%。 实际放电容量 > 260mA /g (其理论放电容量为 333mAh/g )。
实施例 4
第一步, 取 1摩尔碳酸锂 (Li2C03 ); 0.4摩尔乙二酸亚铁; 导电掺杂 剂: 0.12摩尔氧化镁; 增压掺杂剂: 0.24摩尔碳酸锰、 0.24摩尔碱式碳酸 镍, 和 1摩尔纳米 Ti02, 放入 ZrO球磨机中球磨、 搅拌混合 2〜3小时, 碎 第二步, 将第一步制好的粉体压粒后, 放入氧化铝陶瓷坩锅中, 于氮 气 (或氩气)炉中升温至 200〜300°C , 恒温烧结 2〜3小时;
第三步, 冷却至室温后取出, 加入 0.04摩尔石墨烯; 球磨成粉体、 搅 拌均匀;
第四步, 将第三步得到的粉体压粒后, 在氮气 (或氩气) 炉中继续升 温至 500〜650°C , 恒温烧结 8〜15小时, 自然降温至室温;
第五步, 将结晶团块压碎至粉末状;
第六步, 将第五步制备的粉末在超微气流粉碎机上进行破碎和分级, 制成纳米级掺杂二次电池正极材料, 颗粒直径为 40〜80nm。
本实施例制得的掺杂二次电池正极材料经 XRD检测及分析,其结构式 为: Li2[Fe。.4(Mg。.2Mn。.4Ni。.4)。.6]TiO4/C0.04
经测定, 普通锂铁锰钛酸盐正极材料电导率为 3 X 10_13S/cm, 室温放 电平均电压为 3.7V; 而本实施例提供的纳米级掺杂二次电池正极材料的室 温电导率和室温放电电压分别为 1.30 x 10_2S/cm和 4.2V, 分别提高了 1011 倍和 13.51%。 实际放电容量 > 260mAh/g (其理论放电容量为 328mAh/g )。
实施例 5
第一步, 取 1摩尔碳酸钠 (Na2C03 ); 0.95摩尔乙二酸锌; 导电掺杂 剂: 0.01摩尔氧化钙; 增压掺杂剂: 0.02摩尔碳酸锰、 0.02摩尔碱式碳酸 镍, 和 1摩尔纳米 Si02, 放入 ZrO球磨机中球磨、 搅拌混合 2〜3小时, 碎 第二步, 将第一步制好的粉体压粒后, 放入氧化铝陶瓷坩锅中, 于氮 气 (或氩气)炉中升温至 200〜300°C , 恒温烧结 2〜3小时;
第三步, 冷却至室温后取出, 加入 0.03摩尔石墨烯; 球磨成粉体、 搅 拌均匀;
第四步, 将第三步得到的粉体压粒后, 在氮气 (或氩气) 炉中继续升 温至 650〜800°C , 恒温烧结 8〜15小时, 自然降温至室温;
第五步, 将结晶团块压碎至粉末状;
第六步, 将第五步制备的粉末在超微气流粉碎机上进行破碎和分级, 制成纳米级掺杂二次电池正极材料, 颗粒直径为 40〜80nm。
本实施例制得的掺杂二次电池正极材料经 XRD检测及分析,其结构式 为: Na2[Zn0.95(Ca0.2Mn0.4Ni0.4)0.05]SiO4/C0.03。
经测定, 普通钠锰硅酸盐正极材料电导率为 3 x lO-uS/cm, 室温放电 平均电压为 2.7V; 而本实施例提供的纳米级掺杂二次电池正极材料的室温 电导率和室温放电电压分别为 1.30 x 10_2S/cm和 4.0V,分别提高了 109倍和 48%。 实际放电容量 > 250mAh/g。
实施例 6
第一步,取 1摩尔碳酸钾(K2C03 ); 0.5摩尔乙二酸亚铁; 导电掺杂剂: 0.05摩尔氧化钙、 0.05摩尔氧化镁; 增压掺杂剂: 0.2摩尔碳酸锰、 0.2摩 尔碱式碳酸镍,和 1摩尔纳米 Si02,放入 ZrO球磨机中球磨、搅拌混合 2〜3 第二步, 将第一步制好的粉体压粒后, 放入氧化铝陶瓷坩锅中, 于氮 气 (或氩气)炉中升温至 200〜300°C , 恒温烧结 2〜3小时;
第三步, 冷却至室温后取出, 加入 0.03摩尔石墨烯; 球磨成粉体、 搅 拌均匀;
第四步, 将第三步得到的粉体压粒后, 在氮气 (或氩气) 炉中继续升 温至 650〜800°C , 恒温烧结 8〜15小时, 生成掺杂纳米钠钛锰硅酸盐晶体, 自然降温至室温;
第五步, 将结晶团块压碎至粉末状;
第六步, 将第五步制备的粉末在超微气流粉碎机上进行破碎和分级, 制成纳米级掺杂二次电池正极材料, 颗粒直径为 40〜80nm。
本实施例制得的掺杂二次电池正极材料经 XRD检测及分析,其结构式 为: K^Feo.s Cao.iMgfuMn^Nio^o.^SiC Co.o
经测定, 普通钾锰硅酸盐正极材料电导率为 3 X 10-uS/cm, 室温放电
平均电压为 2.7V; 而本实施例提供的纳米级掺杂二次电池正极材料的室温 电导率和室温放电电压分别为 1.30 x 10_2S/cm和 4.0V,分别提高了 109倍和 48% 。 实际放电容量 > 245mAh/g。
本发明实施例 1〜6提供的纳米级掺杂二次电池正极材料可以 0.1C〜10C 的速率快速充电、 30C的速率快速放电, 充电寿命超过 4000次, 其中实施 例 1〜4的实际放电容量超过 260mAh/g。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例, 本发 明的保护范围不限于此。 本技术领域的技术人员在本发明基础上所作的等 同替代或变换, 均在本发明的保护范围之内。 本发明的保护范围以权利要 求书为准。
Claims
1、 一种掺杂二次电池正极材料, 其特征在于, 所述掺杂二次电池正极 材料以碱金属盐为基材, 掺有导电掺杂离子和增压掺杂离子, 其化学通式 为:
A2[Bm(DxE1-x)1-m]F/Cy
其中, A为碱金属离子中的一种; B为正二价金属离子中的一种或其两 种以上任意组合; C为碳; D为导电掺杂离子, 其为 Mg2+、 Ca2+ 、 Sr2+、 Nd2+、 Sm2+或 Eu2+中的一种或其两种以上任意组合; E为增压掺杂离子, 其 为 Mn2+、 Ni2+、 Co2+、 Cu2+或 Zn2+中的一种或其两种以上任意组合; F为负 4价阴离子;
x = 0〜0.3 , m = 0.05〜0.95, y =0.01〜0.06。
2、 根据权利要求 1所述的掺杂二次电池正极材料, 其特征在于, 所述 A为 Li+、 Na+或 K
3、 根据权利要求 1所述的掺杂二次电池正极材料, 其特征在于, 所述 Β为 Fe2+、 Mn2+、 Cu2+、 Zn2+、 V2+、 Sn2+、 W2+、 Mo2+、 Ni2+、 Co2+、 Cr2+、 Ti2+或 Pb2+中的一种或其两种以上任意组合。
4、 根据权利要求 1所述的掺杂二次电池正极材料, 其特征在于, 所述 B为 Fe2+。
5、 根据权利要求 1所述的掺杂二次电池正极材料, 其特征在于, 所述 F为 Si04 4—、 Ti04 4—或 Ge04 4—。
6、 根据权利要求 1所述的掺杂二次电池正极材料, 其特征在于, 所述 掺杂二次电池正极材料的颗粒直径为 40〜80 nm。
7、 权利要求 1〜6任一项所述的掺杂二次电池正极材料的制备方法, 其 特征在于, 包括如下步骤:
1 )计算所需原料量, 取原料: 碱金属盐, 正二价金属的盐, 导电掺杂 剂, 增压掺杂剂和阴离子原料化合物, 混合均匀;
2 )将步骤 1 )得到的粉体压粒后, 在惰性气体环境下, 在 200〜300°C 恒温烧结 2〜3小时;
3 )将步骤 2 )得到的产物冷却至室温, 加入碳源, 碎成粉体、 混合均
匀;
4 )将步骤 3 )所得粉体压粒后,在惰性气体环境下,升温到 500〜800°C , 恒温烧结 8〜15小时;
5 )将步骤 5所得冷却至室温, 粉碎, 即得。
8、 根据权利要求 7所述的制备方法, 其特征在于, 步骤 1 ) 中, 各原 料的摩尔比为: 碱金属盐中碱金属离子: [二价金属的盐中金属离子 + (导 电掺杂剂 +增压掺杂剂 ) ]: 阴离子原料化合物: 碳源中碳元素 = 2:1 :1:0.01-0.06, 其中, 二价金属的盐中金属离子: (导电掺杂剂 +增压掺杂 剂)=0.05〜0.95:0.95〜0.05 ,导电掺杂剂:增压掺杂剂的摩尔比为 0〜0.3:0.7〜1。
9、 根据权利要求 7 所述的制备方法, 其特征在于, 所述碱金属盐为 A(Ac)、 A2C03或 A2C204。
10、 根据权利要求 7所述的制备方法, 其特征在于, 所述正二价金属 的盐为 B(Ac)2 、 BC03或 BC204。
11、 根据权利要求 7所述的制备方法, 其特征在于, 所述导电掺杂剂 为 Mg2+、 Ca2+ 、 Sr2+ 、 Nd2+、 Sm2+或 Eu2+的化合物或其两种以上任意混合
12、 根据权利要求 7所述的制备方法, 其特征在于, 所述增压掺杂剂 为 Ni2+、 Mn2+、 Co2+ 、 Cu2+或 Zn2+的化合物或其两种以上任意混合物。
13、 根据权利要求 7所述的制备方法, 其特征在于, 所述阴离子原料 化合物为 Si(OC2¾)4、 Ti(OC2¾)4、 Ge(OC2¾)4、 硅酸、 钛酸、 锗酸、 Si02、 Ti02或 Ge02。
14、 根据权利要求 7所述的制备方法, 其特征在于, 所述碳源为葡萄 糖或石墨烯。
15、 根据权利要求 7所述的制备方法, 其特征在于, 步骤 1 )中原料的 混合方法为:
取原料: 碱金属盐: A(Ac)或 A2C03或 A2C204, 二价金属的盐: B(Ac)2 或 BC03或 BC204, 导电掺杂剂, 增压掺杂剂和阴离子原料化合物, 在球磨 机中碎成粉体。
16、 根据权利要求 7所述的制备方法, 其特征在于, 步骤 1 )中原料的
混合方法为:
取原料: 碱金属盐: A(Ac)或 A2C03或 A2C204, 二价金属的盐: B(Ac)2 或 BC03或 BC204, 导电掺杂剂, 增压掺杂剂和阴离子原料化合物, 放入配 有水和乙醇的回流系统中, 80°C搅拌 20〜24小时, 烘干备用。
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