WO2014014913A2 - High voltage cathode compositions for lithium-ion batteries - Google Patents
High voltage cathode compositions for lithium-ion batteries Download PDFInfo
- Publication number
- WO2014014913A2 WO2014014913A2 PCT/US2013/050683 US2013050683W WO2014014913A2 WO 2014014913 A2 WO2014014913 A2 WO 2014014913A2 US 2013050683 W US2013050683 W US 2013050683W WO 2014014913 A2 WO2014014913 A2 WO 2014014913A2
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- WIPO (PCT)
- Prior art keywords
- lithium
- composition
- transition metal
- metal oxide
- cathode
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 14
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 37
- 239000011572 manganese Substances 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- 239000010406 cathode material Substances 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- 150000003624 transition metals Chemical group 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- -1 for example Chemical class 0.000 description 3
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- 238000013459 approach Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 150000004692 metal hydroxides Chemical class 0.000 description 2
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910013724 M(OH)2 Inorganic materials 0.000 description 1
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- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 229910000676 Si alloy Inorganic materials 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241000364021 Tulsa Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical compound COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910021350 transition metal silicide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/56—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO3]2-, e.g. Li2[NixMn1-xO3], Li2[MyNixMn1-x-yO3
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present disclosure relates to compositions useful as cathodes for lithium-ion batteries.
- cathode compositions particularly 03 type structured lithium transition metal oxides including nickel (Ni), cobalt (Co), and manganese (Mn).
- the composition has an 03 type structure.
- the composition has an 03 type structure.
- the 03 type structured lithium transition metal oxides deliver the highest volumetric energy at 1C rate between 2.5-4.7V at 30°C.
- Figure 1 is a graph of composited energy at 1C rate between 2.5 -4.7V vs Li/Li+ at 30°C vs. Co and Ni/Mn for the samples of Table 1.
- Figures 2A-2C are cross section contour plots of composited volumetric energy at 1C and Li/M values of 1.03, 1.115 and 1.2, respectively, vs. Co and Ni/Mn.
- High energy lithium ion batteries require higher volumetric energy electrode materials than conventional lithium ion batteries.
- metal alloy anode materials into batteries, because such anode materials have high reversible capacity (much higher than conventional graphite), cathode materials of commensurately high capacity are desirable.
- LiCo0 2 has been widely used in commercial lithium ion batteries. LiCo0 2 , however, cannot cycle well beyond 4.5V and has other drawbacks associated with Co dissolution.
- the lithium transition metal oxide compositions of the present disclosure may include Ni, Mn, and Co.
- compositions of the preceding embodiments may be in the form of a single phase having an 03 crystal structure.
- the compositions may not undergo a phase
- the present disclosure also features lithium- ion batteries incorporating these compositions in combination with an anode and an electrolyte.
- the phrase"03 type structure refers to a lithium metal oxide composition having a crystal structure consisting of alternating layers of lithium atoms, transition metal atoms and oxygen atoms.
- the transition metal atoms are located in octahedral sites between oxygen layers, making a M02 sheet, and the M02 sheets are separated by layers of the alkali metals such as Li. They are classified in this way: the structures of layered AxM02 bronzes into groups (P2, 02, 06, P3, 03).
- the letter indicates the site coordination of the alkali metal A (prismatic (P) or octahedral (O)) and the number gives the number of M02 sheets (M) transition metal) in the unit cell.
- the 03 type structure is generally described in Zhonghua Lu, R. A. Donaberger, and J. R. Dahn, Superlattice Ordering of Mn, Ni, and Co in Layered Alkali Transition Metal Oxides with P2, P3, and 03 Structures, Chem. Mater. 2000, 12, 3583-3590, which is incorporated by reference herein in its entirety.
- a-NaFe0 2 (R-3m) structure is an 03 type structure (super lattice ordering in the transition metal layers often reduces its symmetry group to C2/m).
- the terminology 03 structure is also frequently used referring to the layered oxygen structure found in LiCo0 2 .
- compositions of the present disclosure have the formulae set forth above.
- the formulae themselves reflect certain criteria that have been discovered and are useful for maximizing performance.
- the compositions adopt an 03 crystal structure featuring layers generally arranged in the sequence lithium-oxygen-metal-oxygen-lithium. This crystal structure is retained when the composition is incorporated in a lithium-ion battery and cycled for at least 40 full charge-discharge cycles at 30°C and a final capacity of above 130 mAh/g using a discharge current of 30 mA/g, rather than transforming into a spinel-type crystal structure under these conditions.
- the present disclosure further relates to methods of making the above-described cathode compositions.
- the cathode compositions of the present disclosure may be synthesized by jet milling or by combining precursors of the metal elements (e.g., hydroxides, nitrates, and the like), followed by heating to generate the cathode composition. Heating may be conducted in air at temperatures of at least about 600°C or at least 800°C. The ability to conduct the heating process in air may be desirable because it obviates the need and associated expense of maintaining an inert atmosphere.
- the cathode composition and selected additives such as binders (e.g., polymeric binders), conductive diluents (e.g., carbon), fillers, adhesion promoters, thickening agents for coating viscosity modification such as carboxymethylcellulose or other additives known by those skilled in the art can be mixed in a suitable coating solvent such as water or N-methylpyrrolidinone (NMP) to form a coating dispersion or coating mixture.
- binders e.g., polymeric binders
- conductive diluents e.g., carbon
- fillers e.g., fillers, adhesion promoters, thickening agents for coating viscosity modification such as carboxymethylcellulose or other additives known by those skilled in the art
- NMP N-methylpyrrolidinone
- the coating dispersion or coating mixture can be mixed thoroughly and then applied to a foil current collector by any appropriate coating technique such as knife coating, notched bar coating, dip coating, spray coating, electrospray coating, or gravure coating.
- the current collectors can be thin foils of conductive metals such as, for example, copper, aluminum, stainless steel, or nickel foil.
- the slurry can be coated onto the current collector foil and then allowed to dry in air followed by drying in a heated oven, typically at about 80 C C to about 300°C for about an hour to remove all of the solvent.
- the present disclosure further relates to lithium-ion batteries.
- the cathode compositions of the present disclosure can be combined with an anode and an electrolyte to form a lithium-ion battery.
- suitable anodes include lithium metal, carbonaceous materials, silicon alloy compositions, and lithium alloy compositions.
- Exemplary carbonaceous materials can include synthetic graphites such as mesocarbon microbeads (MCMB) (available from E-One Moli/Energy Canada Ltd., Vancouver, BC), SLP30 (available from TimCal Ltd., Bodio Switzerland), natural graphites and hard carbons.
- Useful anode materials can also include alloy powders or thin films. Such alloys may include electrochemically active components such as silicon, tin, aluminum, gallium, indium, lead, bismuth, and zinc and may also comprise electrochemically inactive components such as iron, cobalt, transition metal silicides and transition metal aluminides.
- the lithium-ion batteries of the present disclosure can contain an electrolyte.
- Representative electrolytes can be in the form of a solid, liquid or gel.
- Exemplary solid electrolytes include polymeric media such as polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, fluorine-containing copolymers, polyacrylonitrile, combinations thereof and other solid media that will be familiar to those skilled in the art.
- liquid electrolytes examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate, .gamma.-butylrolactone, methyl difluoroacetate, ethyl difluoroacetate, dimethoxyethane, diglyme (bis(2-methoxyethyl) ether), tetrahydrofuran, dioxolane, combinations thereof and other media that will be familiar to those skilled in the art.
- the electrolyte can be provided with a lithium electrolyte salt.
- the electrolyte can include other additives that will familiar to those skilled in the art.
- lithium-ion batteries of the present disclosure can be made by taking at least one each of a positive electrode and a negative electrode as described above and placing them in an electrolyte.
- a microporous separator such as CELGARD 2400 microporous material, available from Celgard LLC, Charlotte, N.C., may be used to prevent the contact of the negative electrode directly with the positive electrode.
- Lithium metal oxide material was dispersed in N-methylpyrrolidone (NMP) solvent (from Aldrich Chemical Co.) together with Super P conductive carbon black (from MMM Carbon, Belgium) and polyvinylidine difluoride (PVDF) (from Aldrich Chemical Co.) to form a cathode dispersion composed of 90 weight percent oxide, 5 weight percent Super P and 5 weight percent of PVDF.
- NMP N-methylpyrrolidone
- PVDF polyvinylidine difluoride
- the dispersion was coated on aluminum foil using a stainless steel coating bar, and dried at 110°C for 4 hours to form a composite cathode coating.
- the active cathode loading was about 8mg/cm 2 .
- the cathode material was incorporated into 2325 coin cell half cells in a conventional manner with metallic lithium foil as the counter electrode.
- One layer of CELGARD 2325 microporous membrane (PP/PE/PP) (25 micron thickness, from Celgard, Charlotte, North Carolina) was used to separate the cathode and Li foil.
- Lithium hexafluorophosphate LiPF6
- the coin cells were cycled using a Maccor series 2000 Cell cycler (available from Maccor Inc. Tulsa, Oklahoma, USA) at a temperature of 30°C between 2.5 V and 4.7 V vs. Li/Li+.
- the composited volumetric energy of a composition is defined as 75% of the gravimetric energy (energy/active mass) times the true density (0.75(gravimetric energy X true density)) (maintaining a porosity of 25% in the electrode).
- the energy retention (Energy vs cycle number) of each cathode for the first 40 cycles can be fitted with a linear line. The slope indicates the fading. The flatter curve indicates better fade and therefore higher slope.
- the highest composited volumetric energy at 1C rate among the sintering conditions and Li/M ratios was selected, and its composited volumetric energy at 1C (from 4.7V to 2.5V at 30oC) was plotted in a contour plot vs.
- Ni/Mn and Co using commercial Software Surfer 8 with Kriging Gridding method (from Golden Software, Inc) (shown in Fig.1).
- two sets of composition ranges were observed that deliver the highest volumetric energy at 1C rate between 2.5-4.7V at 30°C: (i) (Ni/Mn ⁇ 1.25; Co ⁇ 0.2); and (ii) (Ni/Mn ⁇ 0.7;Co ⁇ 0.05).
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EP13744892.4A EP2875540A2 (en) | 2012-07-20 | 2013-07-16 | High voltage cathode compositions for lithium-ion batteries |
KR1020157003979A KR20150032743A (en) | 2012-07-20 | 2013-07-16 | High voltage cathode compositions for lithium-ion batteries |
JP2015523182A JP2015528789A (en) | 2012-07-20 | 2013-07-16 | High voltage cathode composition for lithium ion battery |
US14/415,755 US20150180030A1 (en) | 2012-07-20 | 2013-07-16 | High voltage cathode compositions for lithium-ion batteries |
US14/601,579 US20150243981A1 (en) | 2012-07-20 | 2015-01-21 | High voltage cathode compositions for lithium-ion batteries |
US15/223,786 US9601771B2 (en) | 2012-07-20 | 2016-07-29 | High voltage cathode compositions for lithium-ion batteries |
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US14/601,579 Division US20150243981A1 (en) | 2012-07-20 | 2015-01-21 | High voltage cathode compositions for lithium-ion batteries |
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Also Published As
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WO2014014913A3 (en) | 2014-03-20 |
JP2015528789A (en) | 2015-10-01 |
EP2875540A2 (en) | 2015-05-27 |
US20150180030A1 (en) | 2015-06-25 |
KR20150032743A (en) | 2015-03-27 |
US20150243981A1 (en) | 2015-08-27 |
US9601771B2 (en) | 2017-03-21 |
US20160336596A1 (en) | 2016-11-17 |
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