EP2529434A1 - Electrode for a secondary lithium ion battery, free of conductive additive - Google Patents
Electrode for a secondary lithium ion battery, free of conductive additiveInfo
- Publication number
- EP2529434A1 EP2529434A1 EP11701271A EP11701271A EP2529434A1 EP 2529434 A1 EP2529434 A1 EP 2529434A1 EP 11701271 A EP11701271 A EP 11701271A EP 11701271 A EP11701271 A EP 11701271A EP 2529434 A1 EP2529434 A1 EP 2529434A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- electrode
- active material
- particle size
- electrode according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 239000002482 conductive additive Substances 0.000 title abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 50
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011149 active material Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000011164 primary particle Substances 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 230000002902 bimodal effect Effects 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 19
- 239000010936 titanium Substances 0.000 description 16
- 238000009472 formulation Methods 0.000 description 14
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052596 spinel Inorganic materials 0.000 description 11
- 239000011029 spinel Substances 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010450 olivine Substances 0.000 description 6
- 229910052609 olivine Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 5
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 5
- -1 Transition metal cations Chemical class 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910052566 spinel group Inorganic materials 0.000 description 4
- 229910015243 LiMg Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052742 iron Inorganic materials 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
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012425 Li3Fe2 (PO4)3 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010689 LiFePC Inorganic materials 0.000 description 1
- 229910013391 LizN Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ZTOZIUYGNMLJES-UHFFFAOYSA-K [Li+].[C+4].[Fe+2].[O-]P([O-])([O-])=O Chemical compound [Li+].[C+4].[Fe+2].[O-]P([O-])([O-])=O ZTOZIUYGNMLJES-UHFFFAOYSA-K 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical class [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- H01M4/485—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
-
- 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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a Leitschzusatztransport electrode with a lithium titanate as the active material and a secondary lithium ion battery containing them.
- Lithium titanium spinel has been proposed for some time particularly as a substitute for graphite as an anode material in rechargeable lithium ion batteries.
- An up-to-date overview of anode materials in such batteries can be found e.g. in: Bruce et al. .
- Li 4 Ti 5 0i2 compared to graphite are in particular its better cycle stability, its better thermal stability and higher reliability.
- Li 4 Ti 5 0i 2 has a relatively constant potential difference of 1.55 V to lithium and reaches several 1000 charging and discharging cycles with a capacity loss of ⁇ 20%.
- lithium titanate shows a much more positive potential than graphite, which has traditionally been used as an anode in rechargeable lithium-ion batteries.
- the higher potential also results in a lower voltage difference.
- Li 4 Ti 5 0i 2 has a long life and is non-toxic and therefore not harmful to the environment
- Li 4 Ti 5 O 2 The preparation of lithium titanate Li 4 Ti 5 O 2 is described in detail in many respects. Usually, Li 4 Ti 5 0i 2 by means of a solid state reaction between a
- Titanium compound typically TiO 2 , and one
- Lithium compound typically L1 2 CO 3 , at high
- sol-gel method DE 103 19 464 AI
- Lithium titanates can also be provided with a carbon-containing coating (EP 1 796 189 A2).
- the material density of lithium titanium spinel is comparatively low (3.5 g / cm 3 ) compared to, for example, lithium manganese spinel or lithium cobalt oxide (4 or 5 g / cm 3 ), referred to as
- lithium titanium spinel (containing only Ti 4+ ) is an electronic insulator, therefore, in
- a conductive additive such as e.g.
- Acetylene black, carbon black, Ketjen black, etc. is necessary to ensure the necessary electronic conductivity of the electrode. This reduces the energy density of batteries with lithium titanium spinel anodes. However, it is also known that lithium titanium spinel in its reduced state (in its "charged” form containing Ti 3+ and Ti 4+ ) becomes a nearly metallic conductor, which would require a significant increase in the electronic conductivity of the entire electrode.
- LiFePO 4 has recently been used as the cathode material in lithium-ion batteries, so that, for example, a voltage difference of 2 V can be achieved in a combination of Li 4 Ti 5 O 2 and LiFePO 4 .
- non-doped or doped mixed lithium transition metal phosphates with ordered or modified olivine structure or NASICON structure such as LiFeP0 4 ,
- LiMnPO 4 , LiCoPO 4 , LiMnFePO 4 , Li 3 Fe 2 (PO 4 ) 3 were first reported by Goodenough et al. (US 5,910,382, US 6,514,640) as
- lithium titanate must always be mixed with a conductive additive as described in more detail above, before it can be processed into electrode formulations.
- lithium transition metal phosphate or vanadate, as well as lithium titanium spinel carbon composites are proposed which, however, always require the addition of a conductive agent due to their low carbon content.
- EP 1 193 784, EP 1 193 785 and EP 1 193 786 describe so-called carbon composite materials of LiFePC 1 and amorphous carbon, which are used in the production of the
- Iron sulfate and to prevent the oxidation of Fe 2+ to Fe 3+ serves.
- the addition of carbon should also the
- EP 1 193 786 states that carbon must be contained in a content of not less than 3% by weight in the lithium iron phosphate carbon composite in order to provide the necessary capacity and cycle characteristics necessary for a well-functioning
- the object of the present invention was therefore to include electrodes containing lithium titanium spinel as active material with a higher specific load capacity (W / kg or W / 1) and an increased specific energy density for
- this object is achieved by a
- Leitschzusatztransport electrode with a lithium titanate as active material has been found that it is possible to dispense with the addition of conducting agents, such as carbon black, acetylene black, ketal black graphite etc., in the formulation of an electrode according to the invention without impairing their functionality. This was all the more surprising since, as stated above, the lithium titanium spinels are typically insulators.
- additive-free also includes in the present case that small amounts of carbon in the
- Formulation e.g. by a carbonaceous coating or in the form of a lithium titananate-carbon composite material or also as a powder, e.g. in the form of
- Graphite, carbon black, etc. may be present, but these do not exceed a proportion of at most 1.5 wt .-%, preferably at most 1 wt .-%, more preferably at most 0.5 wt .-%.
- lithium titanate-carbon composite material herein means that carbon is uniform in the
- Lithium titanate is distributed and forms a matrix, i. the carbon particles may e.g. form nucleation sites for lithium titanate in situ synthesis.
- carbonaceous composite material is defined, for example, in EP 1 391 424 A1 and EP 1 094 532 A1 on here
- lithium titanate or
- Lithium titanium spinel all lithium titanium spinels of the type
- a lithium titanate means a doped or undoped lithium titanate as defined above
- the lithium titanate used according to the invention is phase-pure.
- phase-pure or
- phase-pure lithium titanate means that no rutile phase can be detected in the end product by means of XRD measurements within the usual accuracy of measurement.
- Very particularly preferred is aluminum.
- the doped lithium titanium spinels are also particularly preferred
- the doping metal ions which can either sit on lattice sites of titanium or lithium, are preferably present in an amount of 0.05 to 10 wt .-%, preferably 1-3 wt .-%, based on the total spinel present.
- the electrode has a content of active material of> 94 wt .-%, more preferably of> 96 wt .-%. Even with these high levels of active mass in the
- electrode according to the invention is not limited their functionality. Surprisingly, it has been found in the present case that a polymodal primary particle size distribution of the active material, ie the lithium titanate, leads to an improved material density and increased capacity density of an inventive material
- Active material by the polymodal particle size distribution by more than 10% higher compared to a purely monomodal
- the primary particles can also be in the form of
- Agglomerates (secondary particles) are present.
- the active material of the electrode according to the invention is preferably a mixture of lithium titanates with
- the shaking density of such a material is, for example, more than 0.7 g / cm 3 .
- the first maximum is the
- Primary particle size distribution at a primary particle size of 100-300 nm (finely divided lithium titanate), preferably 100-200 nm and the second maximum at a primary particle size of 2-3 ⁇ (ds o 2.3 + 0.2 ym, coarse lithium titanate).
- Electrode parameters are achieved when 15 to 40%, preferably 20 to 30% and most preferably 25% ⁇ 1% of all
- Primary particles have a primary particle size of 1-2 ⁇ .
- a part or all of the primary particles of the active material have, in advantageous developments of the present invention, a carbon coating. This is e.g. as described in EP 1 049 182 Bl or DE 10 2008 050 692.3
- the carbon content of the total electrode in this particular embodiment is 1,5 1.5% by weight, preferably ⁇ 1% by weight, and most preferably ⁇ 0.5% by weight, which is well below the prior art cited above previously considered necessary value.
- the electrode according to the invention has an electrode density of> 2 g / cm 3 , more preferably> 2.2 g / cm 3 .
- the electrode according to the invention further contains a binder.
- binders it is possible to use any binder known per se to the person skilled in the art, such as, for example, polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), polyvinylidene difluoride-hexafluoropropylene copolymers (PVDF-HFP), ethylene propylene diene ter polymers (EPDM), tetrafluoroethylene Hexafluoropropylene copolymers, polyethylene oxides (PEO), polyacrylonitriles (PAN), polyacrylmethacrylates (PMMA), carboxymethylcelluloses (CMC), their derivatives, and mixtures thereof.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene difluoride
- PVDF-HFP polyvinylidene difluoride-hexafluoropropylene copolymers
- EPDM ethylene propylene die
- the present invention relates to a
- the cathode can be freely selectable in this embodiment and typically contains one of the known lithium compounds such as lithium manganese spinel,
- Lithium cobalt oxide or a lithium metal phosphate such as
- Lithium iron phosphate, lithium cobalt phosphate, etc. with and without Leitschzusatz Lithium iron phosphate, lithium cobalt phosphate, etc. with and without Leitschzusatz.
- the cathode active material is a doped or non-doped lithium metal phosphate having ordered or modified olivine structure or NASICON structure in a cathode formulation without additive addition.
- Non-doped means that pure, in particular phase-pure lithium metal phosphate is used.
- pure phase is also understood to mean lithium metal phosphates as defined above.
- the lithium transition metal phosphate is represented by the formula wherein N is a metal selected from the group Mg, Zn, Cu, Ti, Zr, Al, Ga, V, Sn, B, Nb, Ca, or mixtures thereof;
- M is a metal selected from the group Fe, Mn, Co, Ni, Cr, Cu, Ti, Ru or mixtures thereof; and with 0 ⁇ x -S 1 and 0 -S y ⁇ 1.
- a doped lithium transition metal phosphate is understood as meaning a compound of the abovementioned formula in which y> 0 and N represents a metal cation from the group such as
- N is selected from the group consisting of Nb, Ti, Zr, B, Mg, Ca, Zn or combinations thereof, but preferably represents Ti, B, Mg, Zn and Nb.
- Typical preferred compounds are, for example LiNb y Fe x P0 4 , LiMg y Fe x P0 4 , LiMg y Fe x Mn 1 - x _ y P0 4 , LiZn y Fe x Mn 1 _ x _ y P0 4 , LiFe x Mn! _ x P0 4 , LiMg y Fe x Mn 1 _ x _ y P0 4 with x and y ⁇ 1 and x + y ⁇ 1.
- the doped or non-doped lithium metal phosphate has, as already stated above, very particularly preferably either one ordered or modified olivine structure.
- lithium metal phosphates in ordered olivine structure can be described in the rhombic space group Pnma (No. 62 of the International Tables), where the
- the crystallographic arrangement of the rhombic unit cell is chosen so that the a-axis is the longest axis and the c-axis is the shortest axis of the unit cell Pnma, so that the mirror plane m of the olivine structure is perpendicular to the b-axis.
- the lithium ions of the lithium metal phosphate in Olivin Design arrange in parallel to
- Modified olivine structure means that modification takes place either on the anionic (e.g., phosphate by vanadate) and / or cationic sites in the crystal lattice, with substitution by aliovalent or like charge carriers to allow for better diffusion of lithium ions and improved electronic conductivity.
- anionic e.g., phosphate by vanadate
- cationic sites in the crystal lattice, with substitution by aliovalent or like charge carriers to allow for better diffusion of lithium ions and improved electronic conductivity.
- the cathode formulation further comprises a second different lithium metal oxygen compound other than the first selected from doped or undoped lithium metal oxides, lithium metal phosphates, lithium metal vanadates, and mixtures thereof.
- lithium-metal-oxygen compounds are included.
- the second lithium-metal-oxygen compound is preferably selected from doped or undoped
- FIG. 1 shows the dependence of the electrode density on the
- Electrode formulation of electrodes of the prior art the dependence of the electrode density of the
- Fig. 3 shows the capacity density of electrodes of the prior
- Coarse lithium titanate (particle size 1-3 ⁇ , abbreviation: LiTi) without and with carbon coating is commercially available from Süd-Chemie AG, Germany under the name EXM1037 or EXM1948. Finely divided lithium titanate (particle size 100-200 nm) without and with
- Carbon coating was produced according to the specification of DE 10 2008 050 692.
- the particle size distribution was determined by means of laser granulometry using a Malvern Mastersizer 2000 apparatus in accordance with DIN 66133.
- the tap density was determined by means of a tamping volumeter STAV II from J. Engelmann AG A graduated cylinder is weighed, attached to the tamping volumeter and then subjected to 3000 strokes, after which the volume is read off and from this the tapped density is determined.
- a standard prior art electrode contained 85% active material, 10% Super P carbon black (Timcal SA, Switzerland) as a conductive additive and 5% by weight polyvinylidene fluoride as a binder (Solvay 21216).
- the standard electrode formulation for the electrode according to the invention was 95% active material and 5% PVdF binder.
- the active material consisted of a mixture of coarse lithium titanate (EXM 1037, abbreviated LiTi) and finely divided lithium titanate (according to DE 10 2008 050 692) each having varying proportions.
- the active material was used together with the binder (or for the electrodes of the prior art with the Leitschzusatz) mixed in N-methylpyrrolidone, on a pretreated
- the primer on the aluminum foil consisted of a light carbon coating which made the electrical contact with the aluminum foil and improved the adhesion of the aluminum foil
- the electrodes were then dried overnight at 120 ° C under vacuum and installed in an argon-filled glove box in half-cells against lithium metal and measured electrochemically.
- EC ethylene carbonate
- DMC dimethyl carbonate
- the test method was carried out in CCCV mode, that is, cycles constant current with the C / 10 rate for the first and the C rate for the subsequent cycles.
- Fig. 1 shows the electrode density as a function of
- Lithium titanate particles of LiTi fills faster.
- the very small particles of Leitschzusatzes also require a high porosity and thus a low electrode density.
- Electrode formulation Again, the ordinate shows the
- Lithium titanate 2 included. The best results are achieved for a range of 25 to 75 parts LiTi in the active composition at loadings of about 5 mg / cm 2 and at lower loadings (2.5 mg / cm 2 ). This may be due to the fact that the small agglomerates of the finely divided lithium titanate better fill the spaces between the particles of the coarse-grained lithium titanate, whereupon the total density of the electrode is increased. The increased electrode density also leads to a
- Figure 3 shows the variation in capacitance density with respect to the proportion of LiTi in a prior art electrode formulation with a 10% additive addition. The best values are obtained here for the formulations, each containing either only coarse lithium titanate or finely divided lithium titanate as the active material.
- Fig. 4 shows that a bimodal
Abstract
Description
Claims
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DE102010006082A DE102010006082A1 (en) | 2010-01-28 | 2010-01-28 | Guide additive-free electrode for a secondary lithium ion battery |
PCT/EP2011/051192 WO2011092277A1 (en) | 2010-01-28 | 2011-01-28 | Electrode for a secondary lithium ion battery, free of conductive additive |
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EP2529434A1 true EP2529434A1 (en) | 2012-12-05 |
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EP11701271A Withdrawn EP2529434A1 (en) | 2010-01-28 | 2011-01-28 | Electrode for a secondary lithium ion battery, free of conductive additive |
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US (1) | US20130108925A1 (en) |
EP (1) | EP2529434A1 (en) |
JP (1) | JP2013518376A (en) |
KR (1) | KR20120132489A (en) |
CN (1) | CN102971894A (en) |
CA (1) | CA2787989A1 (en) |
DE (1) | DE102010006082A1 (en) |
TW (1) | TW201133994A (en) |
WO (1) | WO2011092277A1 (en) |
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DE102011054122A1 (en) * | 2011-09-30 | 2013-04-04 | Westfälische Wilhelms Universität Münster | Electrochemical cell |
CN104508872B (en) * | 2012-05-25 | 2017-04-05 | 加拿大巴斯姆有限公司 | For the electrode material of lithium electrochemical cells |
KR101539843B1 (en) * | 2012-07-13 | 2015-07-27 | 주식회사 엘지화학 | Anode Active Material of High Density and Methode for Preparation of The Same |
EP2784853B1 (en) * | 2013-03-27 | 2018-07-25 | Karlsruher Institut für Technologie | Lithium transistion metal titanate with a spinel structure, method for its manufacturing, its use, Li-ion cell and battery |
JP6385665B2 (en) * | 2013-10-04 | 2018-09-05 | 株式会社東芝 | Cathode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, battery pack and vehicle |
WO2015107832A1 (en) * | 2014-01-16 | 2015-07-23 | 株式会社カネカ | Nonaqueous electrolyte secondary battery and battery pack of same |
US11251430B2 (en) | 2018-03-05 | 2022-02-15 | The Research Foundation For The State University Of New York | ϵ-VOPO4 cathode for lithium ion batteries |
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JP3502118B2 (en) | 1993-03-17 | 2004-03-02 | 松下電器産業株式会社 | Method for producing lithium secondary battery and negative electrode thereof |
US6514640B1 (en) | 1996-04-23 | 2003-02-04 | Board Of Regents, The University Of Texas System | Cathode materials for secondary (rechargeable) lithium batteries |
US5910382A (en) | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
JP2000164217A (en) * | 1998-11-27 | 2000-06-16 | Kyocera Corp | Lithium battery |
KR20010025116A (en) | 1999-04-06 | 2001-03-26 | 이데이 노부유끼 | Method for manufacturing active material of positive plate and method for manufacturing nonaqueous electrolyte secondary cell |
CA2270771A1 (en) | 1999-04-30 | 2000-10-30 | Hydro-Quebec | New electrode materials with high surface conductivity |
JP4768901B2 (en) | 1999-06-03 | 2011-09-07 | チタン工業株式会社 | Lithium titanium composite oxide, method for producing the same, and use thereof |
US6528033B1 (en) | 2000-01-18 | 2003-03-04 | Valence Technology, Inc. | Method of making lithium-containing materials |
JP4734701B2 (en) | 2000-09-29 | 2011-07-27 | ソニー株式会社 | Method for producing positive electrode active material and method for producing non-aqueous electrolyte battery |
JP4734700B2 (en) | 2000-09-29 | 2011-07-27 | ソニー株式会社 | Method for producing positive electrode active material and method for producing non-aqueous electrolyte battery |
JP4491946B2 (en) | 2000-09-29 | 2010-06-30 | ソニー株式会社 | Method for producing positive electrode active material and method for producing non-aqueous electrolyte battery |
JP4780361B2 (en) * | 2000-10-06 | 2011-09-28 | 株式会社豊田中央研究所 | Lithium secondary battery |
CA2394056A1 (en) * | 2002-07-12 | 2004-01-12 | Hydro-Quebec | Particles with a non-conductive or semi-conductive core covered by a conductive layer, the processes for obtaining these particles and their use in electrochemical devices |
US7087348B2 (en) * | 2002-07-26 | 2006-08-08 | A123 Systems, Inc. | Coated electrode particles for composite electrodes and electrochemical cells |
DE10319464A1 (en) | 2003-04-29 | 2004-11-18 | Basf Ag | Process for the production of nanocrystalline lithium titanate spinels |
JP5068660B2 (en) * | 2004-10-29 | 2012-11-07 | メドトロニック,インコーポレイテッド | How to charge a lithium-ion battery |
US7811705B2 (en) * | 2004-10-29 | 2010-10-12 | Medtronic, Inc. | Lithium-ion battery |
US7968231B2 (en) * | 2005-12-23 | 2011-06-28 | U Chicago Argonne, Llc | Electrode materials and lithium battery systems |
US7541016B2 (en) * | 2006-04-11 | 2009-06-02 | Enerdel, Inc. | Lithium titanate and method of forming the same |
FR2902929B1 (en) * | 2006-06-26 | 2009-05-22 | Commissariat Energie Atomique | AQUEOUS DISPERSION BASED ON STARCH AND MIXED OXIDE OF LITHIUM AND TITANIUM, FOR A LITHIUM ACCUMULATOR ELECTRODE. |
CA2569991A1 (en) * | 2006-12-07 | 2008-06-07 | Michel Gauthier | C-treated nanoparticles and agglomerate and composite thereof as transition metal polyanion cathode materials and process for making |
JP5717318B2 (en) * | 2007-02-13 | 2015-05-13 | ナミックス株式会社 | All solid state secondary battery |
US8277683B2 (en) * | 2008-05-30 | 2012-10-02 | Uchicago Argonne, Llc | Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries |
DE102008050692B4 (en) | 2008-10-07 | 2014-04-03 | Süd-Chemie Ip Gmbh & Co. Kg | Carbon-coated lithium titanium spinel |
CN104319383B (en) * | 2009-05-26 | 2018-04-17 | 石原产业株式会社 | Lithium titanate, the method for producing lithium titanate and the electrode active material and electrical storage device for respectively containing lithium titanate |
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- 2011-01-28 JP JP2012550454A patent/JP2013518376A/en active Pending
- 2011-01-28 CA CA2787989A patent/CA2787989A1/en not_active Abandoned
- 2011-01-28 EP EP11701271A patent/EP2529434A1/en not_active Withdrawn
- 2011-01-28 KR KR1020127022369A patent/KR20120132489A/en not_active Application Discontinuation
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TW201133994A (en) | 2011-10-01 |
WO2011092277A1 (en) | 2011-08-04 |
DE102010006082A1 (en) | 2011-08-18 |
US20130108925A1 (en) | 2013-05-02 |
KR20120132489A (en) | 2012-12-05 |
JP2013518376A (en) | 2013-05-20 |
CA2787989A1 (en) | 2011-08-04 |
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