CN103299457B - Phosphate-diphosphate the electrode material of mixing and manufacture method thereof - Google Patents
Phosphate-diphosphate the electrode material of mixing and manufacture method thereof Download PDFInfo
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- CN103299457B CN103299457B CN201180049607.3A CN201180049607A CN103299457B CN 103299457 B CN103299457 B CN 103299457B CN 201180049607 A CN201180049607 A CN 201180049607A CN 103299457 B CN103299457 B CN 103299457B
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- 239000007772 electrode material Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title description 12
- 238000002156 mixing Methods 0.000 title description 5
- BRFMYUCUGXFMIO-UHFFFAOYSA-N OP(O)(O)=O.OP(O)(=O)OP(O)(O)=O Chemical compound OP(O)(O)=O.OP(O)(=O)OP(O)(O)=O BRFMYUCUGXFMIO-UHFFFAOYSA-N 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000001603 reducing Effects 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims description 96
- 229910052720 vanadium Inorganic materials 0.000 claims description 59
- 229910019142 PO4 Inorganic materials 0.000 claims description 53
- 229910052750 molybdenum Inorganic materials 0.000 claims description 46
- XPPKVPWEQAFLFU-UHFFFAOYSA-J Pyrophosphate Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 38
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive Effects 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011651 chromium Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 229910052803 cobalt Inorganic materials 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 12
- 238000007792 addition Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052733 gallium Inorganic materials 0.000 claims description 12
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052732 germanium Inorganic materials 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 12
- 239000011133 lead Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052712 strontium Inorganic materials 0.000 claims description 12
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910015427 Mo2O3 Inorganic materials 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000001177 diphosphate Substances 0.000 claims description 7
- 235000011180 diphosphates Nutrition 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 230000000630 rising Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N Cesium Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910015651 MoOPO4 Inorganic materials 0.000 claims description 5
- 229910015793 MoP2 Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 150000004712 monophosphates Chemical class 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N D-sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229910003562 H2MoO4 Inorganic materials 0.000 claims description 3
- CZMRCDWAGMRECN-GDQSFJPYSA-N Sucrose Natural products O([C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O1)[C@@]1(CO)[C@H](O)[C@@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-GDQSFJPYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910000351 vanadium(III) sulfate Inorganic materials 0.000 claims description 3
- DIMMBYOINZRKMD-UHFFFAOYSA-N vanadium(5+) Chemical group [V+5] DIMMBYOINZRKMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000005518 electrochemistry Effects 0.000 abstract description 4
- 230000002194 synthesizing Effects 0.000 abstract description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920001774 Perfluoroether Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910010951 LiH2 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N Ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N Lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N Phosphorus pentoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 102000014961 Protein Precursors Human genes 0.000 description 2
- 108010078762 Protein Precursors Proteins 0.000 description 2
- 102000004357 Transferases Human genes 0.000 description 2
- 108090000992 Transferases Proteins 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000002349 favourable Effects 0.000 description 2
- 230000001976 improved Effects 0.000 description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-M Diammonium phosphate Chemical compound [NH4+].[NH4+].[O-]P([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-M 0.000 description 1
- 229910011140 Li2C2 Inorganic materials 0.000 description 1
- 229910011304 Li3V2 Inorganic materials 0.000 description 1
- 229910000949 MnO2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003213 activating Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 230000001808 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 101710031899 moon Proteins 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 230000002085 persistent Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atoms Chemical group 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001737 promoting Effects 0.000 description 1
- 230000002441 reversible Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Abstract
The present invention relates generally to electrode material, the electrochemistry single cell using this material and the method synthesizing this material.Described electrode material has the structure having high Li to the ratio of metal M, finds that it improves capacity by making each metal can shift more substantial lithium, and also finds that it improves stability by keeping the lithium of q.s after charging.Further it is proposed that cause the charge/discharge capacity of the raising of electrode material and the synthetic technology of the granularity of reduction.
Description
Quoting of related application
This application claims on August 16th, 2010 submit to U.S. Patent Application Serial 12/857,262 priority and
Rights and interests, by with reference to being integrally incorporated herein.
Technical field
The present invention relates generally to the electrode material improved.More particularly, in some embodiments, the present invention relates to electrode
Material, uses the electrochemistry single cell (electrochemical cell, electrochemical cells) of this material and synthesizes this material
The method of material.
Background technology
Battery has an electrochemistry single cell, and described electrochemistry single cell generally includes positive pole, negative pole and electrolyte.One
Planting battery, lithium ion battery has important technology and commercial Application.At present, lithium ion battery is for portable electric appts
The principal mode of energy storage medium, and novel application such as motor vehicle driven by mixed power and electric vehicle can further improve
Their requirement.Therefore, continue to seek the material component of the improvement for lithium ion battery, and a kind of this component is battery
Positive pole.New electrode materials has the raising capacity of lithium ion battery, high rate performance, cycle performance, stability and safety, and
The probability of their cost may be reduced potentially.
Present electrode material such as LiCoO2, LiFePO4And LiMn2O4Suffer that finite capacity, safety be limited, stability
Some limited, high rate performance finite sum cost is high mixing.Need have than the present more preferable capacity of material, safety, times
Rate performance and the electrode material of stability, and it still can manufacture in industry.
Summary of the invention
The present invention relates to the electrode material with the crystal structure of the ratio uniqueness of high Li and metal M, such as, positive pole
And/or negative material.Present electrode material such as LiCoO2, LiFePO4And LiMn2O4Each metal only allows transferase 10 .5-1
Li.On the contrary, the preferred implementation of electrode material specifically described herein has wherein that Li:M ratio is more than 1:1, and such as, ratio is 3:
The crystal structure of 1, it allows 3 Li of the highest exchange of each metal.It is described herein the success of the experimental example of these materials
Preparation and test.
Because the amount of the electric charge that can shift in electrode material depends on the amount of the Li existed, and because of electrode material
Weight and cost greatly depend on tenor, so crystal structure specifically described herein allows to shift high Li for low amount of metal
Amount.Therefore, electrode material specifically described herein can be with low weight and be realized with a low cost big charging capacity.And, in charging
After, having now been found that the electrode material with low Li:M ratio may keep insufficient amount of lithium, this causes stability problem.Carry herein
The new electrode materials gone out improves capacity not only by making each metal can shift more substantial lithium, and by filling
The lithium of q.s is kept to improve stability after electricity.The lithium thinking remaining after removing active lithium is formed crystal structure
The combination network that certain layer keeps together, thus prevent the decomposition of electrode material.
The vanadium also being characterized as active redox pair of electrode material specifically described herein, molybdenum or vanadium and the group of molybdenum
Close.Find vanadium and molybdenum uniquely can respectively in the limit less than current industrial electrolysis matter, for example, less than about 4.6-4.7V's
Under voltage, support two electron reactions and three electron reactions.Think when in crystal structure specifically described herein, other metals
As Cr, Mn, Fe and Co cause Tai Gao can not support two electron reactions and the voltage of three electron reactions.When by these other metals
When the electrolyte in lithium ion battery current with can be used for major part is used together, this is particularly true.
The method that the invention still further relates to prepare electrode material specifically described herein.There is presented herein cause specifically described herein
The charge/discharge capacity of raising of electrode material and the synthetic technology of granularity of reduction.Described technology allows also to use relatively low conjunction
Become temperature, thus reduce manufacturing cost.
In an aspect, the present invention relates to comprise Li9(V,Mo)3(P2O7)3(PO4)2Electrode material.At particular implementation
In mode, electrode material comprises at least one adulterant in the group of choosing freely following composition: nickel, cobalt, manganese, ferrum, titanium, copper, silver,
Magnesium, calcium, strontium, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum, niobium, zirconium, fluorine, sulfur, yttrium, tungsten, silicon and lead.(V, Mo) can be V, Mo, or V
Combination in any with Mo.In one embodiment, (V, Mo) is V.In another embodiment, (V, Mo) is Mo.Above-mentioned
The explanation of the key element of embodiment can also be applied to the present aspect of the present invention.
In one aspect of the method, electrode material comprises A9-3xM3+x(P2O7)3-y/4(PO4)2+y/3, wherein A is that choosing is as follows
At least one in the group of composition: lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium and barium, wherein A is the Li of at least 50mol%, and M is choosing
At least one in the group of following composition: vanadium, molybdenum, nickel, cobalt, manganese, ferrum, titanium, copper, silver, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum,
Niobium, zirconium, yttrium, tungsten, silicon and lead, wherein M is that at least 50mol% (V, Mo), x are about-0.2 to about 0.2, and y is about-1.0
To about 1.0.In certain embodiments, A is Li.In one embodiment, x is 0 and y to be 0.At another embodiment
In, M is V.In still further embodiment, M is Mo.The explanation of the key element of above-mentioned embodiment can also be applied to the present invention
Present aspect.
In one aspect of the method, electrode material includes [(V, the Mo) (P separated by lithium ion2O7)3(PO4)2]9-The moon from
Sub-corrugated layer (corrugated layer).In certain embodiments, corrugated layer each self-contained (V, Mo) O6Octahedron, described
(V,Mo)O6Octahedron each has and monophosphate (PO4) and diphosphate (P2O7) group share turning (oxygen).At one
In embodiment, (V, Mo) O6Octahedra each self-contained: (a) and a diphosphate (P2O7) group share first and second
Adjacent oxygen, (b) and two monophosphate (PO4) the third and fourth oxygen of sharing of group, and (c) and two diphosphate (P2O7)
The the 5th and the 6th oxygen that group shares.In another embodiment, during electrode material comprises the group of the following composition of choosing
At least one adulterant: nickel, cobalt, manganese, ferrum, titanium, copper, silver, magnesium, calcium, strontium, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum, niobium, zirconium, fluorine,
Sulfur, yttrium, tungsten, silicon and lead.The explanation of the key element of above-mentioned embodiment can also be applied to the present aspect of the present invention.
In one aspect of the method, electrode material comprises LiaMbDc(P2O7)d(PO4)e, during wherein M is vanadium (V) and molybdenum (Mo)
At least one, D is at least one in the group of the following composition of choosing: lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, nickel, cobalt,
Manganese, ferrum, titanium, copper, silver, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum, niobium, zirconium, fluorine, sulfur, yttrium, tungsten, silicon and lead, 5≤a≤12,1.5≤b
≤ 4,0≤c≤1.5,2.75≤d≤3.25 and 1.67≤e≤2.33.In one embodiment, a=9, b=3, c=0, d
=3 and e=2.In another embodiment, M is V.In still further embodiment, M is Mo.Wanting of above-mentioned embodiment
The explanation of element can also be applied to the present aspect of the present invention.
In one aspect of the method, preparation Li9(V,Mo)3(P2O7)3(PO4)2Method comprise the following steps: (a) reaction
Container makes Li2CO3, NH4H2PO4With V2O5, V2O3, NH4VO3, V (SO4)7H2O, V2(SO4)3With VO (SO4)2H2In O at least one
Planting and contact to manufacture mixture, (b) exposes the mixture to reducing gas and (c) at the temperature (high temperature) raised to mixture
Heating, the temperature of wherein said rising is about 300 DEG C to about 950 DEG C.In one embodiment, step (a) include with
The mol ratio of x:y:z makes Li2CO3, NH4H2PO4And V2O5Contact, wherein x is about 4.2 to about 4.8, and y is about 7.8 to about 8.2 and z
It is about 1.3 to about 1.7.In another embodiment, x is about 9, and y is about 16, and z is about 3.In still further embodiment
In, described reducing gas includes at least one in the group of the following composition of choosing: H2, He, Ne and Ar.Implement in further
In mode, described reducing gas is about 0% to about 10%H2The mixture of about 90% to about 100%Ar.Real in further
Executing in mode, described temperature is about 600 DEG C to about 850 DEG C.The explanation of the key element of above-mentioned embodiment can also be applied to this
Bright present aspect.
In one aspect of the method, it is provided that the method manufacturing granule, described method comprises the following steps: that (a) preparation comprises
Li9(V,Mo)3(P2O7)3(PO4)2Material and (b) described material is ground with manufacture there is about 50nm to about 20 micron
The granule of average diameter.Such as, this method preferably obtains less granule.In one embodiment, step (b) includes
Described material is carried out ball milling.In another embodiment, described method includes introducing additive to provide described granule
Conductive coating.In still further embodiment, during the grinding during the heat treatment in step (a) or in step (b),
Or carry out introducing additive during both.In still further embodiment, described additive comprises the following composition of choosing
Group at least one: white carbon black, electric conductivity high-purity carbon black, cellulose ethanoate and sucrose.The key element of above-mentioned embodiment
Explanation can also be applied to the present aspect of the present invention.
In one embodiment, described average diameter is about 1 micron to about 20 microns.In another embodiment,
Described method include introduce interground addition to reduce granularity, wherein said interground addition comprises white carbon black.Real in further
Executing in mode, described interground addition comprises electric conductivity high-purity carbon black.In still further embodiment, described grinding is added
The use of agent allows to the heat treatment carrying out in step (a) at a lower temperature.The explanation of the key element of above-mentioned embodiment
The present aspect of the present invention can also be applied to.
In one aspect of the method, preparation Li9(V,Mo)3(P2O7)3(PO4)2Method comprise the following steps: (a) reaction
Container makes Li2CO3, NH4H2PO4With Mo2O3, MoO2, MoP2O7, MoOPO4, Mo, H2MoO4And MoO3In at least one contact
To manufacture mixture, (b) exposes the mixture to reducing gas, and mixture is carried out at the temperature (high temperature) raised by (c)
Heating, the temperature of wherein said rising is about 550 DEG C to about 1000 DEG C.In certain embodiments, step (a) includes with x:y:
The mol ratio of z makes Li2CO3, NH4H2PO4And Mo2O3Contact, wherein x is about 4.2 to about 4.8, and y is about 7.8 to about 8.2, and z
It is about 1.3 to about 1.7.In one embodiment, x is about 9, and y is about 16, and z is about 3.In another embodiment,
Described reducing gas includes at least one in the group of the following composition of choosing: H2, He, Ne and Ar.Further embodiment party
In formula, described reducing gas is about 0% to about 10%H2The mixture of about 90% to about 100%Ar.Implement in further
In mode, described temperature is about 600 DEG C to about 850 DEG C.The explanation of the key element of above-mentioned embodiment can also be applied to the present invention
Present aspect.
In one aspect of the method, the one during lithium battery comprises above-mentioned electrode material.In certain embodiments, described lithium
Battery is configured such that at least one reduction in the group that run duration general choosing free V, Mo and (V, the Mo) of battery form.
The explanation of the key element of above-mentioned embodiment can also be applied to the present aspect of the present invention.
In further aspect, the compositions of material comprises Li9V3(P2O7)3(PO4)2。
Accompanying drawing explanation
The purpose of the present invention and feature be may be better understood with reference to following drawings and claims.Accompanying drawing need not be by rule
Certainty ratio, and be emphasized when being that typically in the principle of the explanation present invention.In the drawings, identical in whole places of each figure
Numeral is for indicating identical parts.
Although herein with reference to specific embodiment and detailed description of the invention the present invention having been carried out special display and having described,
Although it will be understood by those skilled in the art that without departing from the spirit and scope of the present invention, shape can be carried out wherein
Formula and the various changes of details.
Fig. 1 a and 1b shows the figure of the crystal structure of compound according to an illustrative embodiment of the invention.
Fig. 2 shows the electrochemical profiles calculating prediction of vanadium compositions according to an illustrative embodiment of the invention
Figure.
Fig. 3 shows the electrochemical profiles calculating prediction of molybdenum compositions according to an illustrative embodiment of the invention
Figure.
Fig. 4 is the flow chart of the method illustrating preparation compositions according to an illustrative embodiment of the invention.
Fig. 5 is the flow chart illustrating the method preparing granule according to an illustrative embodiment of the invention.
Fig. 6 is the figure of the X-ray diffractogram illustrating compositions according to an illustrative embodiment of the invention.
Fig. 7 is that the voltage of vanadium compositions according to an illustrative embodiment of the invention is relative to the capacity under C/20 multiplying power
Curve chart.
Fig. 8 is the scanning electron micrograph of vanadium material according to an illustrative embodiment of the invention.
Fig. 9 is that the voltage of vanadium compositions according to an illustrative embodiment of the invention is relative to the capacity under C/20 multiplying power
Curve chart.
Figure 10 is the scanning electron micrograph of vanadium material according to an illustrative embodiment of the invention.
Figure 11 is that the voltage of vanadium material according to an illustrative embodiment of the invention is relative to the capacity under C/20 multiplying power
Curve chart.
Figure 12 is the scanning electron micrograph of vanadium material according to an illustrative embodiment of the invention.
Detailed description of the invention
It is specifically described herein that the compositions of the invention required by expection, mixture, system, method and technique include that use derives from
The variant of information development of embodiment and reorganization.Compositions, mixture, system, method and technique specifically described herein
Reorganization and/or variant can be carried out by those of ordinary skill in the related art.
System is described as having, include or comprising concrete component wherein, or wherein technique and method is described as
Have, include or comprise in all places in the description of concrete steps, it is contemplated that additionally, exist substantially by described component
Composition or the system of the present invention being made up of described component, and exist and be substantially made up of or by described described process step
The process according to the invention of reason step composition and method.
Similarly, wherein mixture and compositions are described as having, include or comprise actual mixt and/or material
In the case of, it is contemplated that additionally, exist and be substantially made up of described compound and/or material or by described compound and/or material
The mixture of the present invention of material composition and compositions.
The order that should be understood that step or the order carrying out specific behavior are inessential, as long as making the present invention keep
Can run.Furthermore, it is possible to carry out two or more step or behavior simultaneously.
Background section is such as be arbitrarily disclosed in mentioning and do not recognize that described disclosure is relative to herein herein
Any claim proposed serves as prior art.Bring out Background technology segment only for clear and its be not intended as relative to
The arbitrarily explanation of the prior art of claim.
There is presented herein a kind of compositions Li9(V,Mo)3(P2O7)3(PO4)2, in its positive pole to such as lithium battery
Application provides favourable performance.In this symbol, (V, Mo) is any mixture of V, Mo, or V and Mo.Such as, when (V,
When Mo) being V, described compositions is to have formula Li9V3(P2O7)3(PO4)2Vanadium compositions.When (V, Mo) is Mo, described combination
Thing is to have formula Li9Mo3(P2O7)3(PO4)2Molybdenum compositions.
In certain embodiments, described compositions comprises the adulterant of such as one or more metallic elements.At some
In embodiment, adulterant is nickel, cobalt, manganese, ferrum, titanium, copper, silver, magnesium, calcium, strontium, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum, niobium, zirconium,
Fluorine, sulfur, yttrium, tungsten, silicon, and/or lead.
It is also proposed following combination thing herein, it provides favourable property to the application in the positive pole of such as lithium battery
Can:
A9-3xM3+x(P2O7)3-y/4(PO4)2+y/3
Wherein A is one or more metals, and M is one or more metals, and x is about-0.2 to be about-1 to about to about 0.2 and y
1.In some embodiments, A is the Li of at least 50%, and M is V, Mo of at least 50%, or their mixture.Replaceable
Ground, A is at least 60,70, Li and/or M of 80,90, or 100% is at least 60,70, V, Mo of 80,90, or 100%, or they
Mixture.A and/or M can also include one or more adulterants, such as, such as, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium,
Nickel, cobalt, manganese, ferrum, titanium, copper, silver, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum, niobium, zirconium, yttrium, tungsten, silicon and lead.In particular implementation
In, A is Li and/or M is V, Mo, or their mixture, x and/or y can be zero.
Fig. 1 a and 1b shows the figure of the crystal structure 100 of the compound according to exemplary embodiment of the invention.Institute
State compositions and there is the structure belonging to P-3c1 (165) space group.As depicted, described structure includes being separated by lithium ion 110
[(V, Mo) (P2O7)3(PO4)2]9-Continuous print anion corrugated layer.Described layer comprises (V, Mo) O6Octahedra 120, described
(V,Mo)O6Octahedron and monophosphate (PO4) and diphosphate (P2O7) group 130 shares turning (that is, oxygen).From MO6Octahedral
Two adjacent oxygen 140 of body and a P2O7Group shares.Two other oxygen 140 and two other P2O7Group connects, and two
Residue oxygen 140 and two PO4Group shares.As depicted, PO4And P2O7Group 130 is around the tetrahedron of phosphorus atoms 150.
(V, Mo) atom 160 is positioned at (V, Mo) O6In octahedra 120.
Fig. 2 and 3 is to respectively illustrate under the density functional theory framework with+U correction being applied to transition metal
The figure of the electrochemical profiles calculating prediction of vanadium compositions and molybdenum compositions.Described compositions is advantageously able to support two electron back
Should be with the voltage of the limit (being i.e. below about 4.6 to 4.7V) less than current industrial electrolysis matter.In the case of vanadium, available two
Individual redox couple (V3+/4+And V4+/5+), and in the case of molybdenum, available three redox couple (Mo3+/4+, Mo4+/5+With
Mo5+/6+).When together with electrolyte in most of present lithium ion battery, Li9M3(P2O7)3(PO4)2Other join
Side's (such as, wherein M is Cr, Mn, Fe or Co) causes Tai Gao can not support the voltage of two electron reactions.When M is Mn, pass through
Use 3+/4+ redox couple can implement an electron reaction, but this reaction can cause the poor theoretical capacity of-85mAh/g.
The crystal structure of compositions is unique in terms of its lithium with the height ratio of metal, and it allows each vanadium and/or molybdenum the highest
Exchange 3 lithiums.Because the amount of the electric charge that can shift in electrode material depends on the amount of the lithium existed in the material, so institute
State compositions and structure advantageouslys allow for shifting high lithium amount for low amount of metal.Further, since the weight of electrode material with become
Originally tenor is greatly depended on, so described compositions provides the probability realizing big charging capacity with low weight and cost.
The most each metal transfer is less than in the case of 3 lithiums, and such as, the M=V of the most each V transferase 12 Li joins
Fang Zhong, crystal structure can comprise the Li of some remnants after charging.The Li of these remnants is formed after charging by [(M (P2O7)3
(PO4)2]9-The combination network that layer keeps together.Therefore, the Li of excess serves as [(M (P after removing activity Li2O7)3
(PO4)2]9-The stabiliser kept together, thus prevent the decomposition of material.This embedded stabiliser is to be proposed
The another kind of specific characteristic of crystal structure.
Using the calculating instruction that the density functional theory with+U correction is carried out, described compositions has following character: flat
All voltage is for V3+/4+Redox couple is about 3.9V and for V4+/5+Redox couple is about 4.4V；Use two oxidations also
The former theoretical energy density to (theoretical capacity is 173mAh/g) is 725Wh/kg and 1916Wh/I；Good interpolation property is (only
The most metastable de-lithium state)；With the quite stable released relative to oxygen, can with currently used as lithium ion cell positive
MnO2Spinel compound is compared.
Fig. 4 depicts for preparing compositions Li9(V,Mo)3(P2O7)3(PO4)2Method 200, described method is included in
Reactor makes precursor mixing or contact to manufacture mixture (step 210), expose the mixture to reducing gas (step 220)
At elevated temperatures mixture is heated (step 230).Carry out step 220 and 230 the most simultaneously.Precursor includes one
Plant or multiple containing lithium precursor, one or more phosphorous precursors, one or more precursors Han vanadium, and/or one or more are containing before molybdenum
Body.The possible precursor containing lithium includes Li2CO3, Li3PO4, LiH2PO4, LiOH, LiNO3, LiF, Li2C2O4, Li (CH3COO) and
Li4P2O7.Possible phosphorous precursor includes NH4H2PO4, Li3PO4, MoP2O7, MoOPO4, NH4VO3, LiH2PO4, (NH4)2HPO4,
H3PO4, P2O5, Li4P2O7And LiH2PO4.The possible precursor containing vanadium includes V2O5, V2O3, NH4VO3, V (SO4)7H2O, V2(SO4)3With
VO(SO4)2H2O.The possible precursor containing molybdenum includes Mo2O3, MoO2, MoP2O7, MoOPO4, Mo, H2MoO4And MoO3。
It is such as Li for preparing the precursor of vanadium compositions2CO3, NH4H2PO4And V2O3And/or V2O5.In step 210,
Such as, Li is made with the mol ratio of x:y:z2CO3, NH4H2PO4And V2O5Contact, wherein x is about 4.2 to about 4.8, y be about 7.8 to
About 8.2, and z is about 1.3 to about 1.7.In one embodiment, x is about 9, and y is about 16 and z to be about 3.
It is such as preparing the precursor of molybdenum compositions, Li2CO3, NH4H2PO4And Mo2O3And/or MoO2.In step 21O
In, such as, make Li with the mol ratio of x:y:z2CO3, NH4H2PO4And Mo2O3Contact, wherein x is about 4.2 to about 4.8, and y is about
7.8 to about 8.2, and z is about 1.3 to about 1.5.In certain embodiments, x is about 9, and y is about 16, and z is about 3.
Alternatively, use and lithium, phosphorus, the precursor of at least two in vanadium and molybdenum are provided.The example of this precursor includes
Li3PO4, MoP2O7And MoOPO4。
In a step 220, reducing gas is such as H2, He, Ne, and/or Ar.In certain embodiments, reducing gas
It is about 0% to about 10%H2The mixture of about 90% to about 100%Ar.Such as, reducing gas can be about 5%H2Peace treaty
95%Ar, or about 3%H2The mixture of about 97%Ar.
In step 230, the temperature of rising is about 300 DEG C to about 1000 DEG C.Such as, the temperature of rising be about 550 DEG C extremely
About 850 DEG C or about 800 DEG C.For the most about 3 hours to about 48 hours, or such as, the response time of about 12 hours, in step
In 230, mixture is heated.
Fig. 5 depicts the method 300 of the smaller particle manufacturing the electric conductivity with raising.Described method includes: preparation bag
Containing Li9(V,Mo)3(P2O7)3(PO4)2Material (step 310) and be ground manufacturing granule (step to described material
320).Grinding can be such as high-energy ball milling.In order to manufacture less granule, can be in step 310 and/or step 320 phase
Between add interground addition such as SUPERCarbon (electric conductivity high-purity carbon black), and/or cellulose ethanoate.Gained granule is permissible
There is about 50nm to about 20 micron, or the average diameter of about 1 micron to about 20 microns.Described interground addition can allow relatively
The heat treatment in step 310 is carried out under low temperature.
In order to provide conductive coating to granule, introduce such as, white carbon black, SUPERCarbon, and/or the additive (step of sucrose
Rapid 330).Can introduce between heat treatment in step 230 and/or during period and/or ball milling in step 320 and add
Agent.Additive is by promoting that electron conduction improves the chemical property of material.When introducing additive before the heat treatment
Time, in addition to improving electron conduction, it also has to reduce to be formed expects the effect of temperature necessary to material.Relatively low temperature
Spend and also cause granularity to decline.In some embodiments, add PTFE binding agent with by material together with additive adhesion,
Described material and additive typically dry powder and may not adhering to each other independently.Electrode can comprise such as,
80wt% active material, 15wt% white carbon black and 5wt%PTFE binding agent.
Additive, interground addition and grinding technics self are used for realizing two purposes: (a) reduces granularity and (b) carries
High electron conduction.Material can be ground in the case of not having additive by purpose (a) by after high-temperature process
And realize.Material can be ground by utilizing additive and/or interground addition and realize by purpose (a) and (b).Can replace
Change ground, and may more effectively, purpose (a) and (b) can be by utilizing additive and/or grinding before carrying out high-temperature process
Mill additive is ground and realizes.Utilize this latter to select, after body but mixing precursor is being added before combination
It is ground before heat.
In certain embodiments, described compositions is used as electrochemical appliance such as the electrode material in lithium battery.Excellent
In the embodiment of choosing, electrode material is positive electrode.
EXPERIMENTAL EXAMPLE
Embodiment 1. uses and is placed in the ZrO with a diameter of 3-11mm2Stoichiometric amount in the 250ml hermetically sealed can of ball
Precursor Li2CO3, NH4H2PO4, V2O5, on Paul O.Abbe Inc. ball mill (JRM type) at 300RPM under utilize acetone
Ball milling 48 hours, prepares vanadium compositions by solid-state reaction, utilizes stirring rod to be dried it under heating plate, until obtaining
Dry powder, pelletize, heat in atmosphere at 300 DEG C 6 hours in Lindberg/Blue batch-type furnace, utilize mortar and pestle
Regrinding, pelletize, and at reducing gas (97%Ar, 3%H in Lindberg/Blue tube furnace2) steady flow under,
Again heat at 800 DEG C 24 hours.The Li of trace is detected in final powder4P2O7And Li3V2(PO4)2。
Fig. 6 shows the X-ray using the Rigaku final powder of Miniflex Diffractometer with Cr source
Diffraction (XRD) figure, and show relative to Li9Fe3(P2O7)3(PO4)2Fe composition XRD coupling.With reference to this figure, preparation
Vanadium compositions show the crystal structure identical with Fe composition.
Embodiment 2. uses and includes that following specified program is to prepare vanadium compositions: (1) stoichiometrically ratio makes precursor
Li2CO3, V2O5And NH4H2PO4Contact；(2) ball milling 48 hours in acetone under 300RPM；(3) hand-ground, pelletize and
In air at 300 DEG C heat treatment 6 hours；(4) hand-ground, pelletize at 97%Ar, 3%H2In at 800 DEG C at heat
Manage 24 hours.Under substantially C/20 multiplying power, perfluoro alkoxy (PFA) SWAGELOK monocell (part#PFA-820-6) is carried out
Test.Total positive pole weight in each monocell is 2.2-2.3mg.Fig. 7 is the vanadium compositions using this specified program to prepare
Voltage is relative to the curve chart of the capacity under C/20 multiplying power.As depicted, the voltage window of 3-5V achieves about 85mAh/g
The first discharge capacity.With reference to Fig. 8, the granularity of material is about 5 microns to about 20 microns.
Embodiment 3. uses and includes that following carbon coating processes prepares vanadium compositions: (1) stoichiometrically ratio makes precursor
Li2CO3, V2O5And NH4H2PO4Contact；(2) powder is placed in there are 3 10mm stainless steel balls and 15 3mm stainless steel balls
In 50ml rustless steel bottle, and in RetschPM 200 planetary ball mill at 400RPM under by precursor mix 12 hours；(3)
Hand-ground, pelletize heat treatment 6 hours at 300 DEG C in atmosphere；(4) hand-ground, pelletize at 97%Ar, 3%H2
In at 800 DEG C heat treatment 12 hours；(5) under 400RPM, 15%SUPER is utilizedCarbon (by weight) is at planetary type ball-milling
Machine mixes 6 hours.To perfluoro alkoxy (PFA) SWAGELOK monocell (part#PFA-820-6) under substantially C/20 multiplying power
Test.Total positive pole weight in each monocell is 2.2-2.3mg.Fig. 9 is to use carbon coating processes in embodiment 3 to prepare
The voltage of vanadium compositions relative to the curve chart of the capacity under C/20 multiplying power.As depicted, with use embodiment 2 specified
The vanadium material of program manufacture is compared, and discharge capacity is improved to about 110mAh/g by carbon coating processes from 85mAh/g, and the most greatly
Improve capability retention.As depicted in fig. 10, carbon coating processes creates the granularity of about 2 to about 5 microns.
Embodiment 4. uses and includes that following carbon high-temp reducing program is to prepare vanadium compositions: (1) stoichiometrically ratio will
Precursor Li2CO3, V2O5And NH4H2PO4With 15% (by weight) SUPERCarbon mixes；(2) at planetary ball under 400RPM
Grinding machine mixes 12 hours；(3) hand-ground, pelletize heat treatment 6 hours at 300 DEG C in atmosphere；(4) manually grind
Mill, pelletize at 97%Ar, 3%H2In at 700 DEG C heat treatment 12 hours.Compared with the specified program of embodiment 2, embodiment
The carbon high-temp reducing program of 4 is carried out in relatively low temperature with under the shorter persistent period, is therefore simpler and cheap synthesis
Program.Under substantially C/20 multiplying power, perfluoro alkoxy (PFA) SWAGELOK monocell (part#PFA-820-6) is tested.
Total positive pole weight in each monocell is 2.2-2.3mg.Figure 11 is the electricity of the vanadium material using carbon high-temp reducing program to prepare
Press the curve chart relative to the capacity under C/20 multiplying power.As depicted, the chemical property of resulting materials and the specified journey of use
The chemical property of the material that sequence manufactures is similar to.With reference to Figure 12, the scanning electron micrograph of the material of carbon high-temp reduction synthesis
Showing the evidence of primary particle and second particle, wherein primary particle granularity is 5 to 15 microns and second particle granularity
It is about 1 micron.
With reference to Fig. 7,9 and 11, the result instruction of embodiment 2,3 and 4, the theoretical capacity of 173mAh/g can be easily achieved
Half.Fig. 9 shows the reversible capacity exceeding half theoretical capacity.It addition, Fig. 7 and 11 show with for V4+/5+Oxidation
Activity under the voltage that the voltage to calculating prediction that reduces is close.Therefore, test proves, can be by two oxygen in this material
Change and reduce to activating veritably, and whole theoretical capacities can be obtained by further optimizing.
About the reaction pressure for above-described embodiment, piths of these reactions are frequently not gross pressure, but oxygen
Changing intensity, it is controlled by the dividing potential drop of reducing gas.Under normal atmospheric pressure, carry out experiment itself, but they can also be
Carrying out under the pressure limit of non-constant width, condition is to keep oxidizing intensity by having suitable reducing gas ratio.Therefore, exist
The most conventional solid-state synthesizes as in above-described embodiment, it is stipulated that be admixture of gas rather than gross pressure.
Equivalence
Although the present invention has been carried out special display with reference to preferred implementation and has described, but those skilled in the art should
Understand, in the case of without departing substantially from the spirit and scope of the present invention being defined by the appended claims, can carry out wherein
Form and the various changes of details.
Claims (38)
1. an electrode material, comprises Li9(V,Mo)3(P2O7)3(PO4)2, wherein, described electrode material comprise choosing free nickel, cobalt,
Manganese, ferrum, titanium, copper, silver, magnesium, calcium, strontium, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum, niobium, zirconium, fluorine, sulfur, yttrium, tungsten, silicon and the group of lead composition
In at least one adulterant.
Electrode material the most according to claim 1, wherein, (V, Mo) comprises V, Mo, or the combination in any of V and Mo.
Electrode material the most according to claim 1 and 2, wherein, (V, Mo) is V.
Electrode material the most according to claim 1 and 2, wherein (V, Mo) is Mo.
5. an electrode material, comprises:
A9-3xM3+x(P2O7)3-y/4(PO4)2+y/3,
Wherein A is to select free lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, and at least one in the group of strontium and barium composition, wherein A is at least
The Li of 50mol%；
M be select free vanadium, molybdenum, nickel, cobalt, manganese, ferrum, titanium, copper, silver, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum, niobium, zirconium, yttrium, tungsten, silicon with
At least one in the group of lead composition, wherein M is at least 50mol% (V, Mo)；
X is in the range of-0.2 to 0.2；And
Y is in the range of-1.0 to 1.0；
Wherein, described electrode material comprises the free nickel of choosing, cobalt, manganese, ferrum, titanium, and copper is silver-colored, magnesium, calcium, strontium, zinc, aluminum, chromium, gallium, germanium,
Stannum, tantalum, niobium, zirconium, fluorine, sulfur, yttrium, tungsten, at least one adulterant in the group of silicon and lead composition.
Electrode material the most according to claim 5, wherein, A is Li.
7. according to the electrode material described in claim 5 or claim 6, wherein, x is 0 and y to be 0.
Electrode material the most according to claim 5, wherein, M is V.
Electrode material the most according to claim 5, wherein, M is Mo.
10. an electrode material, comprises [(V, the Mo) (P separated by lithium ion2O7)3(PO4)2]9-Anion corrugated layer, its
In, described electrode material comprises the free nickel of choosing, cobalt, manganese, ferrum, titanium, and copper is silver-colored, magnesium, calcium, strontium, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum,
Niobium, zirconium, fluorine, sulfur, yttrium, tungsten, at least one adulterant in the group of silicon and lead composition.
11. electrode materials according to claim 10, wherein, each in described corrugated layer comprises (V, Mo) O6Octahedral
Body, described (V, Mo) O6Octahedron each has and monophosphate (PO4) and diphosphate (P2O7) group share turning
(oxygen).
12. electrode materials according to claim 11, wherein, described (V, Mo) O6Each in octahedron comprises:
(a) and a diphosphate (P2O7) group share first and second adjoin oxygen,
(b) and two monophosphate (PO4) group share the third and fourth oxygen；With
(c) and two diphosphate (P2O7) group share the 5th and the 6th oxygen.
13. 1 kinds of electrode materials, comprise:
LiaMbDc(P2O7)d(PO4)e,
At least one during wherein M is vanadium (V) and molybdenum (Mo)；
D is to select free lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, nickel, cobalt, manganese, ferrum, titanium, copper, silver, zinc, aluminum, chromium, gallium, germanium,
Stannum, tantalum, niobium, zirconium, fluorine, sulfur, yttrium, tungsten, at least one in the group of silicon and lead composition；
5≤a≤12,1.5≤b≤4,0 < c≤1.5,2.75≤d≤3.25, and 1.67≤e≤2.33.
14. electrode materials according to claim 13, wherein, M is V.
15. electrode materials according to claim 13, wherein, M is Mo.
Prepare Li for 16. 1 kinds9V3(P2O7)3(PO4)2Method, said method comprising the steps of:
A () makes Li in reaction vessel2CO3, NH4H2PO4With V2O5, V2O3, NH4VO3, V (SO4)7H2O, V2(SO4)3With VO (SO4)2H2At least one contact in O is to produce mixture；
B described mixture is exposed to reducing gas by ()；And
C described mixture is heated by () at elevated temperatures, the temperature of wherein said rising is 300 DEG C to 950 DEG C；
Wherein, step (a) includes making Li with the mol ratio of x:y:z2CO3, NH4H2PO4And V2O5Contact, wherein x is 4.2 to 4.8, y
It is 7.8 to 8.2, and z is 1.3 to 1.7.
17. methods according to claim 16, wherein, x is 9, and y is 16, and z is 3.
18. according to the method described in claim 16 or 17, and wherein, described reducing gas includes H2With free He, Ne and Ar group of choosing
At least one in the group become.
19. methods according to claim 18, wherein, described reducing gas is greater than 0% and the H of not higher than 10%2No
The mixture of the Ar less than 90%.
20. methods according to claim 16, wherein, described temperature is 600 DEG C to 850 DEG C.
21. 1 kinds of methods producing granule, said method comprising the steps of:
A () preparation comprises Li9(V,Mo)3(P2O7)3(PO4)2Material；With
B described material is ground producing the granule of the average diameter with 50nm to 20 micron by ().
22. methods according to claim 21, wherein, step (b) includes described material is carried out ball milling.
23. according to the method described in claim 21 or claim 22, and wherein, described method includes introducing additive with to institute
State granule and conductive coating is provided.
24. methods according to claim 23, wherein, grinding during the heat treatment in step (a) or in step (b)
During mill, or carry out introducing additive during both.
25. methods according to claim 23, wherein, described additive comprises the free white carbon black of choosing；Electric conductivity high-purity charcoal
Black；Cellulose ethanoate；With at least one in the group of sucrose composition.
26. methods according to claim 21, wherein, described average diameter is 1 micron to 20 microns.
27. methods according to claim 21, described method include introduce interground addition to reduce granularity, wherein said
Interground addition comprises white carbon black.
28. methods according to claim 27, wherein, described interground addition comprises electric conductivity high-purity carbon black.
29. methods according to claim 24, wherein, the use of interground addition allows to enter at a lower temperature
Described heat treatment in row step (a).
Prepare Li for 30. 1 kinds9Mo3(P2O7)3(PO4)2Method, said method comprising the steps of:
A () makes Li in reaction vessel2CO3, NH4H2PO4With Mo2O3, MoO2, MoP2O7, MoOPO4, Mo, H2MoO4And MoO3In
At least one contact is to produce mixture；
B described mixture is exposed to reducing gas by ()；With
C described mixture is heated by () at elevated temperatures, the temperature of wherein said rising is 550 DEG C to 1000 DEG C.
31. methods according to claim 30, wherein, step (a) includes making Li with the mol ratio of x:y:z2CO3,
NH4H2PO4And Mo2O3Contact, wherein x is 4.2 to 4.8, and y is 7.8 to 8.2, and z is 1.3 to 1.7.
32. methods according to claim 31, wherein, x is 9, and y is 16, and z is 3.
33. according to the method according to any one of claim 30 to 32, and wherein, described reducing gas includes H2With select free He,
At least one in the group of Ne and Ar composition.
34. methods according to claim 33, wherein, described reducing gas is greater than 0% and the H of no more than 10%2No
The mixture of the Ar less than 90%.
35. methods according to claim 30, wherein, described temperature is 600 DEG C to 850 DEG C.
36. 1 kinds of lithium batteries, comprise the electrode material according to any one of claim 1 to 15.
37. lithium batteries according to claim 36, described lithium battery is configured such that the run duration at battery will choosing
At least one reduction in the group that free V, Mo and (V, Mo) form.
The compositions of 38. 1 kinds of materials, comprises Li9V3(P2O7)3(PO4)2, wherein, the compositions of described material comprises choosing freely
Nickel, cobalt, manganese, ferrum, titanium, copper, silver, magnesium, calcium, strontium, zinc, aluminum, chromium, gallium, germanium, stannum, tantalum, niobium, zirconium, fluorine, sulfur, yttrium, tungsten, silicon and lead group
At least one adulterant in the group become.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/857,262 | 2010-08-16 | ||
| US12/857,262 US8399130B2 (en) | 2010-08-16 | 2010-08-16 | Mixed phosphate-diphosphate electrode materials and methods of manufacturing same |
| PCT/US2011/031946 WO2012024001A1 (en) | 2010-08-16 | 2011-04-11 | Mixed phosphate-diphosphate electrode materials and methods of manufacturing same |
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| CN1641915A (en) * | 2003-12-18 | 2005-07-20 | 原子能委员会 | Lithium battery showing both high electric potential and lithium intercalation capacity |
| CN101997109A (en) * | 2009-08-20 | 2011-03-30 | 华南理工大学 | Method for preparing lithium-ion battery anode material Li9V3(P2O7)3(PO4)2 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1641915A (en) * | 2003-12-18 | 2005-07-20 | 原子能委员会 | Lithium battery showing both high electric potential and lithium intercalation capacity |
| CN101997109A (en) * | 2009-08-20 | 2011-03-30 | 华南理工大学 | Method for preparing lithium-ion battery anode material Li9V3(P2O7)3(PO4)2 |
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