SE2250851A1 - A cathode active material for a cathode in a battery cell, a cathode assembly for a battery cell and a battery cell - Google Patents
A cathode active material for a cathode in a battery cell, a cathode assembly for a battery cell and a battery cellInfo
- Publication number
- SE2250851A1 SE2250851A1 SE2250851A SE2250851A SE2250851A1 SE 2250851 A1 SE2250851 A1 SE 2250851A1 SE 2250851 A SE2250851 A SE 2250851A SE 2250851 A SE2250851 A SE 2250851A SE 2250851 A1 SE2250851 A1 SE 2250851A1
- Authority
- SE
- Sweden
- Prior art keywords
- cathode
- active material
- battery cell
- cathode active
- assembly
- Prior art date
Links
- 239000006182 cathode active material Substances 0.000 title claims abstract description 31
- 239000002019 doping agent Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000006183 anode active material Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 229940000425 combination drug Drugs 0.000 claims 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 230000001976 improved effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000009830 intercalation Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- -1 ethylene carbonate Chemical class 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003013 cathode binding agent Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- 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
-
- 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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A cathode active material for a cathode in a battery cell, where the cathode active material has the formula LixNiaMnbCocMgdMeCh-yAy, where 0.95<x<1.05, and where a+b+c+d+e=1, where 0.5<a<0.98, and where M is one or more metal dopants selected from the group consisting of Ti4+, Ta5+,Ru8+, Os8+ and Mo6+ and c<0.1, 0.005<d<0.02, 0.01<e<0.05, and wherein A is one or more element selected from the group consisting of S, N, F, CI, Br, I, and P, and y<0.1 . A cathode assembly for a battery cell and a battery cell.
Description
1 A cathode active material for a cathode in a battery cell, a cathode assembly for a battery cell and a battery cell Technical field The present disclosure relates to a cathode active material for a cathode in a battery cell, a cathode assembly for a battery cell and a battery cell. Background art The use of rechargeable (secondary) batteries is becoming increasingly prevalent, due in part to trends in society such as vehicle electrification and pervasive use of mobile consumer electronics. Since their commercial introduction in 1991, lithium ion batteries (Li-ion) batteries have been widely adopted in a variety of applications due to favourable properties such as high energy density, low self-discharge or little or no memory effect. However, there is a continuous desire to develop lithium-ion batteries with improved properties.
A Li-ion battery cell typically comprises a cathode and an anode, with an electrolyte and a sepa rator arranged between the electrodes. Typically, the cathode comprises an intercalation material, which is a solid host network capable of reversibly storing lithium guest ions. Most commercialised cathode materials are based on transition metal oxides, such as the lithium cobalt oxide used in the first commercial lithium ion batteries, where cobalt contributes to stability and performance in the cathode material. The anode typically comprises a carbon material such as graphitic or hard carbon, which is capable of intercalating lithium between its graphene planes. The separator may typically be a single- or multi-layer porous polyolefin membrane, sometimes coated with one or more ceramic layers. Electrolytes for lithium ion batteries may typically be based on organic carbonates such as ethylene carbonate, with additives such as lithium salts used to optimise the electrolyte properties. Summary The inventors have identified a number of shortcomings with prior art lithium ion batteries. ln order to expand the range of applications to which Li-ion batteries are suited, there is a need to improve the cost and performance ofthe batteries. Some appropriate performance metrics that are desirable to be improved include, but are not limited to, charge rate, discharge rate, energy Interna 2 density, specific energy, power density, and specific power of the batteries. Some of the raw materials used in the manufacture of Li-ion batteries are relatively scarce and thus expensive, particularly some of the transition metals used in cathode manufacture, and there is a desire to transition to the use of cheaper, more abundant materials.
NMC is a commonly used intercalation material in cathode active materials for lithium ion batteries, and cobalt may typically be added to the cathode active material to obtain stability in the cathode active material and to obtain improved performance. However, cobalt is both scarce and toxic, and it would therefore be desirable to be able to reduce the cobalt content in the cathode active material, while maintaining stability and performance and avoiding cathode corrosion.
The present disclosure aims at solving this problem by providing a cathode active material for a cathode in a battery cell, where the cathode active material has the formula LiXNiaMnbCocMgdlvleDfOzyAy, where 0.95 0sfs0.05, and wherein A is one or more element selected from the group consisting of S, N, F, Cl, Br, I, and P, and y50.1. The one or more metal dopants may advantageously have an oxidation state of 5 or more, and may preferably be TazOf, or IV|oO3 or a combination thereof.
Preferably, the Ni content in the above formula is 0.83sas0.98.
As will be described in more detail below, the presence of the dopants in combination with magnesium in the cathode active material allows the cobalt content to be reduced, without compromising the performance ofthe cathode active material and the battery cell.
The present disclosure also relates to a cathode assembly for a battery cell, the cathode assembly comprising a current collector and a cathode layer, wherein the cathode layer comprises the cathode active material as described above, and to a battery cell comprising the cathode assembly, an anode assembly comprising a current collector and at least one anode active material layer, a separator, and an electrolyte. The anode active material may preferably comprise graphite, or graphite and a silicon-based material. The electrolyte of the battery cell may preferably comprise one or more organic solvents, preferably ethylene carbonate, ethyl Interna 3 methyl carbonate, and/or dimethyl carbonate, or combinations thereof, more preferably a combination of EC, EI\/IA and DMC, most preferably having a solvent composition EC/EMC/DMC=2/4/4 based on mole weight. Further, the electrolyte may comprise one or more lithium salts, preferably LiPF6 or LiPOZ, or combinations thereof, and/or one or more additives, preferably vinylene carbonate or fluoroethylene carbonate, or combinations thereof.
The present disclosure will become apparent from the detailed description given below. The detailed description and specific examples disclose preferred embodiments ofthe disclosure by way of illustration only. Those skilled in the art understand from guidance in the detailed description that changes and modifications may be made within the scope of the disclosure. Hence, it is to be understood that the herein disclosed disclosure is not limited to the particular component parts of the device described or steps of the methods described since such device and method may vary. lt is also to be understood that the terminology used herein is for purpose of describing particular embodiments only, and is not intended to be limiting. lt should be noted that, as used in the specification and the appended claim, the articles "a", "an", and "the " are intended to mean that there are one or more of the elements unless the context explicitly dictates otherwise. Furthermore, the words "comprising", "including", "containing" and similar wordings does not exclude other elements or steps. Detailed description A lithium ion battery cell comprises at least one cathode assembly, at least one anode assembly, an electrolyte, and optionally a separator. The electrolyte is arranged in contact with the cathode and anode in order to provide ion transport within the cell. The separator, if present, is primarily intended to provide a physical barrier between the cathode and anode, whilst still permitting ion transport. The cell may comprise a single cathode assembly and single anode assembly, or multiple cathodes, i.e. two or more cathodes, and/or multiple anodes, i.e. two or more anodes. The contents ofthe cell may be housed in a casing. The cell may be of any design known in the art, such as a cylindrical, prismatic or pouch cell, and is preferably a cylindrical cell.
Depending on the application, single battery cells may be used, or the cells may be arranged into battery packs comprising a plurality of battery cells, i.e. two or more battery cells, such as from about two to about 20 000 cells. A battery pack may comprise a plurality of cells arranged Interna 4 in series and/or parallel, and may comprise further components such as a battery management system and a pack housing to enclose the battery pack components.
A cathode assembly comprises a current collector and at least one cathode layer, and the current collector may comprise a metal foil, such as an aluminium foil, a copper foil, a stainless steel foil, or combinations thereof. The current collector may preferably be aluminium foil. A cathode layer is arranged on at least one surface of the current collector, alternatively on both surfaces of the current collector. The cathode layer comprises cathode active material, binder, and optionally further additives such as conductive additive, for example a carbon material such as graphitic particles, carbon black, carbon nanotubes (single- or multi-walled) or graphite particles.
NMC is among the most popular cathode materials for lithium ion batteries, due in part to it having a specific energy comparable to lithium cobalt oxide (LCO) despite lower cost. lncreasing the proportion of nickel in the NMC provides further improved energy/power density and may therefore be desirable, but may result in capacity degradation with repeated use. Cobalt is often added to the cathode material in an amount ofabout 10 mole% to obtain stability in the cathode material and obtain improved performance by balancing magnetic frustration. For example in case of NMC 811, the cobalt content is normally 10 mol%. However, cobalt is both scarce and toxic, and it would therefore be desirable to be able to reduce the cobalt content in the cathode active material, while maintaining stability and performance and avoiding cathode corrosion.
Accordingly, the cathode active material for a cathode in a battery cell according to the present disclosure comprises an NMC metal oxide intercalation material, preferably wherein nickel constitutes 5-98 mol%, preferably at least 83 mol%, of the total of non-lithium metals in the NMC metal oxide intercalation material. The cathode active material has the formula LiXNiaMnbCocMgdlvleDfOzyAy, where 0.95 group consisting of S, N, F, Cl, Br, I, and P, and y50.1. The I\/|n content of the cathode active material may suitably be 0.005Sb50.02, and the Co content may preferably be 0.03Sc50.09.
Interna lnclusion of magnesium in the cathode active material can contribute to thermal stability and delay oxygen release, prolonging cycling stability of cathode materials having high Ni content, such as Ni>8O mol%. Battery cells containing Mg-substituted materials with high Ni content have been found to exhibit superior discharge capacities when charged to 4.5 V. While cycle life and thermal stability can be significantly improved by the inclusion of I\/lg in the cathode active material, it may reduce the initial capacities and specific energies, due to I\/lg being electrochemically inactive and occupying Li sites in the layered crystal structure. The I\/lg content should therefore be in the range O,5-2 mol% based on the total of non-lithium metals in the NMC metal oxide intercalation material. lt has further been found that the selected dopa nts Ti4+, Ta5+,Ru8+, Oss* and Ivloö* can contribute to highly oriented, elongated grain microstructures formation due to proper orientation of crystal structure, and reduce the risk of formation of micro-cracks. This can reduce the risk of collapse in structure in a high charge state, and can improve balancing of magnetic moment in case of high nickel content, thus improving stability.
This is especially beneficial for high Ni content NI\/IC-type cathode materials, such as above 80 mol%, which may result in a complex synthesis and several structural instability issues limiting cell cycle life and safety, for example high reactivity toward moisture, lower thermal stability of the charged electrode, Li+/Ni+ cation mixing, phase transformation from layered to inactive rock salt NiO phase, micro-crack formation upon cycling, as well as dissolution of transition metals from NMC and subsequent deposition at the anode.
Thus, the presence of the dopants in combination with magnesium in the cathode active material allows the cobalt content to be reduced, without compromising the performance of the cathode active material. The metal dopants may prefera bly have an oxidation state of 5 or more, for example Ta5+,Ru8+, Oss* and/or I\/|o6+, preferably Ta5+ and/or I\/|o6+, as this gives and improved effect due to improved stabilization of magnetic frustration. TazOf, or IV|oO3 are easily available and less expensive compared to the other dopants, and may thus be preferred.
The present disclosure also relates to a cathode assembly for a battery cell, the cathode assembly comprising a current collector and a cathode layer, wherein the cathode layer comprises the cathode active material as described above. The cathode assembly may be prepared by coating the current collector with a slurry comprising the cathode active material, Interna 6 binder and optional additives in a suitable solvent. A suitable solvent may be a polar aprotic solvent such as NMP (N-methyl-2-pyrrolidone). Any suitable coating methods known in the art may be used. Following the coating, the cathode assembly may be further processed as is conventional in the art, such as by drying and calendaring.
This disclosure further relates to a battery cell comprising a cathode assembly as mentioned above, an anode assembly comprising a current collector and at least one anode active material layer, a separator, and an electrolyte. The current collector may comprise, consist essentially of, or consist of a metal foil, such as a copper foil, an aluminium foil, a stainless steel foil, or combinations thereof. The current collector may preferably be copper. An anode layer is arranged on at least one surface of the current collector, alternatively on both surfaces of the current collector. The anode layer comprises anode active material, binder, and optionally further additives such as conductive additive. The binder may be any binder known in the art, such as for example SBR (styrene-butadiene rubber), CMC (carboxymethylcellulose), PVDF (polyvinylidene fluoride), or combinations thereof. The binder preferably consists essentially of a combination of SBR and CI\/|C. The anode active material may comprise, consist essentially of, or consist of any anode active material known in the art, including but not limited to graphite particles, graphitic carbon particles, amorphous carbon particles, silicon, silicon monoxide, germanium, tin, LTO (lithium titanium oxide), and combinations or composites thereof. The anode active material may consist essentially of graphite and/or graphitic particles, such as carbon-coated natural graphite particles, or secondary synthetic graphite particles.
Alternatively, the anode active material may consist essentially of a composite of graphite and a silicon-based material, such as silicon oxide.
The electrolyte may comprise one or more organic solvents, preferably ethylene carbonate EC, ethyl methyl carbonate EMC, and/or dimethyl carbonate DMC , or combinations thereof, more preferably a combination of EC, EMA and DI\/|C, most preferably having a composition EC/EMC/DMC=2/4/4 based on mole weight.
The electrolyte may preferably comprise one or more lithium salts, preferably LiPF6 or LiPOZ, and/or one or more additives, preferably vinylene carbonate (VC) or fluoroethylene carbonate (FEC), in order to increase the battery cell lifetime by supporting formation of an effective solid Interna 7 electrolyte interphase (SEI) at the anode. For an anode comprising only graphite, same electrolyte can be used, but without FEC.
The person skilled in the art realizes that the present disclosure is not limited to the preferred embodiments described above. The person skilled in the art further realizes that modifications and variations are possible within the scope ofthe appended claims. Additionally, variations to the disclosed embodiments can be understood and effected by the skilled person in practicing the claimed disclosure, from a study ofthe disclosure and the appended claims.
Claims (9)
1. A cathode active material for a cathode in a battery cell, characterised in that the cathode active material has the formula LiXNiaMnbCocMgdlvleDfOzyAy, where 0.95 0.005Sd50.02, 0.01SeS0.05, 0SfS0.05, and wherein A is one or more element selected from the group consisting of S, N, F, Cl, Br, I, and P, and ySO.
2. The cathode active material of claim 1, wherein the one or more metal dopants are selected from the group consisting of Ta5+,Ru8+, Oss* and I\/|o6+.
3. The cathode active material of claim 1 or 2, wherein the one or more metal dopants are introduced as TazOf, or IV|oO3 or a combination thereof.
4. The cathode active material of any one of claims 1-3, wherein 0.83Sa50.
5. A cathode assembly for a battery cell, the cathode assembly comprising a current collector and a cathode layer, wherein the cathode layer comprises the cathode active material according to any one of claims 1-
6. A battery cell comprising a cathode assembly according to claim 5, an anode assembly comprising a current collector and at least one anode active material layer, a separator, and an electrolyte.
7. The battery cell of claim 6, wherein the anode active material comprises graphite, or graphite and a silicon-based material.
8. The battery cell of claim 6 or 7, wherein the electrolyte comprises one or more organic solvents, preferably ethylene carbonate (EC), ethyl methyl carbonate (EMC), and/or dimethyl carbonate (DI\/|C), or combinations thereof, more preferably a combination of EC, EI\/|A and DI\/|C, most preferably having a solvent composition EC/EMC/DMC=2/4/4 based on mole weight. 9
9. The battery cell of claim 8, wherein the electrolyte comprises one or more lithium salts, preferably LiPF6 or LiPOZ, or combinations thereof, and/or one or more additives, prefera bly vinylene ca rbonate (VC) or fluoroethylene carbonate (FEC), or com binations thereof.
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PCT/EP2023/068213 WO2024008636A1 (en) | 2022-07-06 | 2023-07-03 | A cathode active material for a cathode in a battery cell, a cathode assembly for a battery cell and a battery cell |
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US20090186272A1 (en) * | 2008-01-17 | 2009-07-23 | Samsung Sdi Co., Ltd. | Cathode and lithium battery including the same |
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JP2016031881A (en) * | 2014-07-30 | 2016-03-07 | 日立マクセル株式会社 | Nonaqueous electrolyte secondary battery |
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US20110269018A1 (en) * | 2009-06-17 | 2011-11-03 | Satoshi Kono | Electrode for electrochemical device and electrochemical device using the same |
JP2017188428A (en) * | 2016-03-30 | 2017-10-12 | Basf戸田バッテリーマテリアルズ合同会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing the same, and nonaqueous electrolyte secondary battery using the same |
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US20090186272A1 (en) * | 2008-01-17 | 2009-07-23 | Samsung Sdi Co., Ltd. | Cathode and lithium battery including the same |
US20120282524A1 (en) * | 2010-12-20 | 2012-11-08 | Satoshi Kono | Nonaqueous secondary battery |
JP2013254639A (en) * | 2012-06-07 | 2013-12-19 | Hitachi Maxell Ltd | Nonaqueous secondary battery |
JP2016031881A (en) * | 2014-07-30 | 2016-03-07 | 日立マクセル株式会社 | Nonaqueous electrolyte secondary battery |
CN108767239A (en) * | 2018-06-07 | 2018-11-06 | 四川富骅新能源科技有限公司 | A kind of nickelic low cobalt tertiary cathode material and preparation method thereof |
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