EP3847710A1 - Wiederaufladbare lithium-batterie mit einer kompositanode - Google Patents
Wiederaufladbare lithium-batterie mit einer kompositanodeInfo
- Publication number
- EP3847710A1 EP3847710A1 EP19765455.1A EP19765455A EP3847710A1 EP 3847710 A1 EP3847710 A1 EP 3847710A1 EP 19765455 A EP19765455 A EP 19765455A EP 3847710 A1 EP3847710 A1 EP 3847710A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- metal
- transition metal
- compounds
- composite anode
- 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.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 80
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 48
- 150000003624 transition metals Chemical class 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 13
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 11
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 238000003780 insertion Methods 0.000 claims abstract description 5
- 230000037431 insertion Effects 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims abstract description 4
- -1 transition metal nitrides Chemical class 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910017958 MgNH Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 4
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical class [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- 229910000045 transition metal hydride Inorganic materials 0.000 claims description 4
- 229910020091 MgCa Inorganic materials 0.000 claims description 3
- 101100003996 Mus musculus Atrn gene Proteins 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 101100425947 Mus musculus Tnfrsf13b gene Proteins 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910003470 tongbaite Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000011262 electrochemically active material Substances 0.000 claims 1
- 229910001009 interstitial alloy Inorganic materials 0.000 claims 1
- 229910001512 metal fluoride Inorganic materials 0.000 claims 1
- 229910052596 spinel Inorganic materials 0.000 claims 1
- 239000011029 spinel Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 239000010405 anode material Substances 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000010406 cathode material Substances 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- GRQJZSJOACLQOV-UHFFFAOYSA-N [Li].[N] Chemical compound [Li].[N] GRQJZSJOACLQOV-UHFFFAOYSA-N 0.000 description 11
- 239000011575 calcium Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 4
- 229910052845 zircon Inorganic materials 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910009997 Li2Mg Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101100231507 Caenorhabditis elegans ceh-2 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910020194 CeH2 Inorganic materials 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 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
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical group 0.000 description 1
- 108010051489 calin Proteins 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical class [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WAWVSIXKQGJDBE-UHFFFAOYSA-K trilithium thiophosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=S WAWVSIXKQGJDBE-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 1
- 229910000568 zirconium hydride Inorganic materials 0.000 description 1
Classifications
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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
- H01M4/13—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
- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of 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
- H01M4/364—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
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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
-
- 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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- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
Definitions
- the invention relates to a rechargeable lithium battery with a composite anode containing, as an electrochemically active component in the composite anode, a metal nitrogen compound, a cathode separated from it by a separator and containing lithium-insertable compounds and an aprotic lithium electrolyte.
- both the negative electrode (anode) and the positive electrode (cathode) consist of materials that can insert lithium ions without fundamental changes in the microstructure. While a carbon-based material - graphite or hard carbon - is used as the anode material, the cathode active materials consist of transition metal oxides. The transition metals in the latter oxides are redox-active, i.e. they change their oxidation state when loading or unloading. This is demonstrated by the following example reaction:
- LiM + III 0 2 Li + + e- + IV + M 0 2 M metal such as Ni, CO, M. Q unload
- the oxidation level of the redox-active metal centers is only changed by one level when charging / discharging the battery, in the above case the oxidation levels change between +111 and + IV. For this reason, the capacity of the cathode materials is relatively low. In the case of the classic cathode material L1C0O2, the theoretical capacity is 274 mAh / g, of which only approx. 135 mAh / g can be used in practice.
- the graphitic material used for the anode also has a relatively low capacity for the limit stoichiometry LiC6 with 372 mAh / g.
- Lithium ion batteries are based on the fact that the metals used, such as cobalt and nickel, are predominantly used as cathode materials. There is a fear that the metals mentioned will not be available in sufficient quantities to ensure a nationwide supply of lithium batteries for worldwide electromobility and stationary energy storage.
- lithium alloys As the anode material instead of pure lithium metal.
- lithium alloys show extremely large volume fluctuations during lithium storage and retrieval (sometimes several 100%, e.g. LigAL: 238%). Therefore, with the exception of tin-graphite composites, alloy anodes have so far not been able to establish themselves on the market. Tin is toxic and a rare and expensive element, which prevents the widespread use of tin-containing materials.
- Open battery systems are being investigated as an alternative to cation redox active positive electrode materials. These contain a porous structure, usually made of carbon, which is open to the environment and the surface of which is covered with a noble metal-containing catalyst, so that diffused oxygen can be bound to form lithium oxides (oxygen reduction reaction):
- lithium superoxide L1O2
- the oxygen has an average oxidation number of -0.5. Further absorption of lithium produces lithium peroxide (L12O2) with an oxygen oxidation number of -1.
- the the latter lithium oxide can be converted back to lithium and elemental oxygen in the presence of a metal catalyst which catalyzes the oxygen oxidation, in reverse of the formation reaction:
- the air electrode described above has only a very low power density and, above all, only a very limited reversibility, so that this cathode shape is still a long way from being used in commercial batteries.
- the currently insurmountable technical challenges lead to the expectation that the lithium / air battery can only be commercialized in 10 - 20 years at the earliest. For an overview, see K. Amine et al., Chem. Reviews 2014, 561 1 -40, 1 14.
- the object of the invention is to provide a lithium battery which has a high energy density of 500 Wh / kg or more and a good safety characteristic, with no Li metal anode being used. Active materials with the lowest possible content of rare or poorly available metals should also be used.
- M 2 an alkaline earth element selected from the group consisting of Mg, Ca, Sr, Ba or any mixture thereof is with
- a cathode positive electrode which is separated by a separator and contains lithium-insertable compounds selected from metal oxides, lithium metal oxides, lithium oxides and lithium hydroxide and an aprotic lithium electrolyte
- the electrochemically active metal nitrogen compounds of the composite anode being composed of an electronic or mixed-conductive network containing transition metals finely divided transition metals and / or electronically or mixed-conductive interstitial transition metal compounds are embedded, and the weight ratio between the components forming the network and the nitrogen-containing compounds I and / or II is in the range from 1: 100 to 1: 2.
- an electronically or mixed-conductive network is understood to mean a purely electronically conductive or a material that is both ionically and electronically conductive.
- these correspond to the general formulas (III) and / or (IV)
- Cathode materials whose electrochemical potential exceeds a value of about 2 V vs Li / Li + can be used for the cathode.
- Nanoparticulate lithium oxygen compounds selected from lithium hydroxide (LiOH), lithium oxide (L12O), lithium peroxide (L12O2) and lithium superoxide (L1O2), which are embedded in an electronically or mixed-conductive network, are preferred. If LiOH is used, the cathode also contains lithium hydride (LiH) at least after it has been charged for the first time.
- the rechargeable lithium batteries according to the invention have a high reversible storage capacity without the use of metallic lithium or a material capable of alloying with lithium (for example tin, silicon or aluminum) as the anode.
- metallic lithium for example tin, silicon or aluminum
- the principle of operation of the electrochemically active anode materials according to the invention is explained below.
- M 2 has the lowest possible atomic mass, ie M 2 is preferably magnesium (Mg) or calcium (Ca) or a mixture thereof.
- the galvanic element preferably contains one or more of the following compounds as active anode material according to the generic formula (I): U 2 NH, MgNH, CaNH, Li 2 Mg (NH) 2, Li 2 Ca (NH) 2, MgCa (NH) 2, Li 4 Mg (NH) 3, Li2Mg2 (NH) 3 and / or one or more of the following compounds according to the generic formula (II): LiNF, Ca (NFl 2 ) 2 or Mg (NFl 2 ) 2 .
- the active N-containing anode materials change into a lithium-rich state.
- the lithium-rich compounds are formed according to the generic formulas (III), preferably: LLNH, L ⁇ CaNH, L ⁇ MgNH, Li 6 Mg (NH) 2, Li 6 Ca (NH) 2 , Li 4 MgCa (NH) 2 , Lii 0 Mg (NH) 3, Li 8 Mg 2 (NH) 3 and / or according to the generic formula (IV), preferably: L1 3 N, CaLiN, MgLiN and LiH.
- the imide compounds containing more than one metal can be phase-pure compounds such as, for. B.
- Li 4 Mg (NH) 3 which is formally a mixture of Li2Mg (NH) 2 and U2NH (see KJ Michel, AR Akbarzadeh, V. Ozolins, J.Phys.Chem.C. 2009, 1 13, 14551 -8) and Li 2 Mg 2 (NH) 3, a mixed compound of Li2Mg (NH) 2 and MgNH (see E. Weidner et al., J.Phys.Chem. C 2009, 1 13, 15772- 7), known from the literature.
- Sr2LiNFl2 that can be used in the inventive sense as a high capacitance, lithium-nitrogen-based anode material (s. DM Liu, QQLiu, tZSI, QAZhang, Journal of Alloys and Compounds, 495, 9 April 2010. 272-274) lists.
- Lithium amide has the highest lithium absorption capacity of the low-lithium anode active materials according to the invention (see Table 1).
- the specific electrochemical capacity can therefore be increased.
- a 1: 1 mixture of lithium amide and lithium imide, U2NH a theoretical specific capacity of the mixed anode material of 3103 Ah / kg is obtained.
- the electrochemical half reaction of the mixture is described by the following equation:
- L1NH2 can be added by mixing the pure components; however, it is also possible to synthesize a structurally uniform mixed phase Li2-xNHi + x, for example by hydrogenating Li 3 N to the desired H content (see D. Chandra et al., DOE Hydrogen Program, FY 2009 Ann. Moscow. Rep. 477-482).
- the lithium nitrogen-based anode active materials can be produced according to the synthetic routes listed in the patent documents WO 201 1/051290 A1 and WO 201 1/121084 A1.
- the use of lithium nitrogen compounds according to the generic formulas (I), (II), (III) and (IV) as high-capacity anode materials is known from the patents WO 201 1/051290 A1 and WO 201 1/121084 A1.
- both documents specifically stipulate that battery anodes produced with them should not contain any transition metals.
- WO 201 1/121084 A1 does not expressly refer to the absence of transition metals in the anode, but there is no indication of a possible presence of transition metals or transition metal compounds in the negative mass (anode).
- the inventors have found that the lithium nitrogen compounds according to the general generic formulas (I) - (IV) when used according to the technical teachings of WO 201 1/051290 A1 and WO 201 1/121084 A1 as anode materials have only a very low electrochemical capacity and have an almost non-existent reversibility when attempting to cyclize a galvanic cell produced therewith.
- the exact dimensions of the preferred nanoparticulate impression depend on the mechanical form factor (ie the three-dimensional shape of the particles). In the case of spherical (or similar) particle shapes, this is 0.1-100 nm, preferably 1-30 nm.
- the electronic conductivity of the finely divided transition metal powders and / or finely divided conductive ones Transition metal compounds with an electrochemical potential of ⁇ 2.5 V against Li / Li + is at least 10 7 S / cm at room temperature, preferably at least 10 6 S / cm and particularly preferably at least 10 5 S / cm.
- Transition metal compounds with an electrochemical potential of ⁇ 2.5 V against Li / Li + .
- transition metal nitrides nitridometalates
- both binary (MN X , MC X, MH X ) and ternary (MM ' y N x ; MM' y C x ; MM ' y H x ) and higher mixed phases can be used, the further metal M '' at least one further transition metal from the 3rd to 12th group of the periodic table (M x M ' y N z ) and / or the element is lithium (Li y MN x ; Li y MC x ; Li w M x M' y N z ; Li w M x M ' y H z ; etc).
- Nanoparticulate nitridometalates can be produced, for example, by grinding crystalline materials using high-energy mills (planetary ball mills) (DH Gregory, The Chemical Record, Vol. 8, 229-239, 2008). However, they can also be produced by other physical processes such as physical vapor deposition, plasma and laser methods or by chemical processes. The chemical processes generally start from the elemental metals or corresponding compounds (oxides, hydrides, etc.) and provide for reactions with nitrogen sources such as ammonia, cyanamide, urea or gaseous nitrogen, mostly at high temperatures (S. Dong et al., Coordination Chem. Reviews 257 (2013) 1946-56).
- Highly conductive nanoporous transition metal nitrides can be produced, for example, by ammonolysis of Zn- and Cd-containing oxide precursors (M. Yang, J. DiSalvo, Chem. Materials 2012, 24, 4406-9).
- the following transition metal nitride compounds are particularly preferably used: TiN n , ZrNn, HfN n , VN n , NbNn, TaN n , CrNn, MoN n , WN n , MnN n , FeN n , CoN n , NiN n , ZnN n ; Cn.
- Transition metal carbides can be produced by carbothermal reduction, co-reduction processes, flydrothermal processes, sol-gel processes and CVD processes.
- Nanoparticulate carbides with 1 D or 2D morphologies are generally synthesized by template processes (Y. Zong, Adv. Sei. 2016, 3, 1500286). The following are particularly preferred
- Transition metal hydrides are generally produced by flotation of the underlying metals, usually at elevated temperatures and elevated hydrogen pressures (U. Wietelmann, M. Felderhoff, P. Rittmeyer, in: Ullmann's Encyclopedia of Industrial Chemistry, "Hydrides”, A13, 2016, Wiley -VCH, Weinheim).
- the stoichiometries given indicate the highest or highest levels (limit stoichiometries) of carbon, nitrogen or hydrogen.
- interstitial compounds are not exactly stoichiometric compounds, ie generally all compositions starting from the pure metal up to the specified limit stoichiometry are possible and mostly stable. All compounds with lower foreign element contents, that is to say qualitatively represented by Li w M x M ' y E z-5 (d can have any value between 0 and z), are likewise electronically or mixedly conductive materials and therefore for the production of the composite anodes according to the invention with nitrogen-containing active materials suitable.
- nanoparticulate, electronically conductive transition metals and / or their likewise nanoparticulate nitride, carbide or hydride compounds are mixed as homogeneously as possible by means of a physical mixing process with the anode material which also contains nanoparticulate lithium nitrogen, with subsequent pressing (in the case of technical-commercial production calendering) good contacting of the individual particles is guaranteed in the anode strip production and the fully functional composite anode containing nitrogen and transition metal is obtained.
- Composite anode materials according to the invention can also be produced by chemical processes, for example reactions with nitrogen sources. Elemental nitrogen (N 2 ) serves as preferred nitrogen sources; Ammonia (NH3); Hydrazine (N 2 H 4 ); Urea (CH 4 N 2 0).
- the metals that is to say lithium and the corresponding transition metals
- ammonia at preferably elevated temperatures and under pressure.
- the amide compounds obtained can then be converted further by subsequent thermolysis, for example into imide compounds and / or nitrides.
- appropriate transition metal hydrides and / or transition metal carbides selection: see above
- the remaining solids can be ground together. This measure reduces the particle size and improves the contact.
- nitridic phases form immediately. In this case too, desired non-nitridic conductivity improvers can be added.
- the lithium nitrogen-containing anode materials according to the invention are co-ground with the conductivity-improving transition metals or their nitrides, carbides or hydrides.
- a high-energy mill for example of the planetary ball mill type, is used for the grinding.
- non-metal-based conductivity improvers include non-metal-based conductivity improvers, lithium-donating additives and binders.
- a non-metal based conductivity improver especially all conductive forms of elemental carbon (graphite, carbon black, graphene, carbon nanotubes) in question.
- lithium metal preferably coated, that is surface passivated and in powder form or as a thin film
- the organic polymers usually used for the production of electrodes can be used as binders. These include PTFE, PVdF, polyisobutylene (eg Oppanole ® from BASF) and similar materials.
- the finished nitrogen and transition metal-containing composite anode according to the invention may additionally contain further conductivity improvers (0 to 30% by weight), binders (0 to 20% by weight) and / or prelithiating agents (0 to 20% by weight).
- the nitrogen and transition metal-containing composite anode materials according to the invention can in principle be used for the production of rechargeable lithium cells with any counter electrodes.
- the electrochemical potential of the cathode active materials used should be at least 2.0 V, preferably at least 2.5 V vs. the Li / Li + reference electrode.
- the usable cathode materials include in particular lithiated metal oxide insertion materials, preferably layer-structured compounds such as L1C0O2, LiNi02, Li (Ni, Mn, Co) 02, LiNio, 8oCoo, i5Alo, os02 and spinel-structured materials such as LiMn 2 0 4 and LiNio .5 Mni .
- Non-lithiated metal insertion compounds such as electrolytic manganese dioxide (MnÜ2) or vanadium oxides (V2O3) can also be used.
- MnÜ2 electrolytic manganese dioxide
- V2O3 vanadium oxides
- the chemical formulas listed above each indicate the ideal compositions of the basic compounds. In practice, however, these are used in a slightly or more modified form.
- materials with structure-stabilizing doping eg Al-stabilized Li-nickel cobalt oxide, “NCA” or compounds made with foreign metals or non-metals doped for the purpose of increasing the conductivity.
- Such variants of the parent compounds modified by doping can also be used according to the invention. In the sense of the invention it is also possible to use mixtures of different cathode materials.
- a positive electrode the electrochemically active component of which is formed by at least one anion-redox-active material in the form of a lithium oxygen compound, selected from: lithium hydroxide (LiOH), lithium oxide (L12O), lithium peroxide (L12O2) and lithium superoxide (L1O2) , given is.
- a lithium oxygen compound selected from: lithium hydroxide (LiOH), lithium oxide (L12O), lithium peroxide (L12O2) and lithium superoxide (L1O2) , given is.
- the cathode materials used with preference have a capacity which is at least 4 times higher than the theoretical capacity of, for example, L1C0O2.
- lithium oxygen compounds mentioned are electronic insulators, they must be in finely divided (amorphous or nanoparticulate) form and the individual particles must be contacted using an electronically or mixed conductive network.
- conductive, finely divided metals as well as many metal oxides and lithium metal oxides can be used.
- Such systems are known from the literature and only exemplary embodiments are mentioned here.
- Lithium peroxide, L12O2 can be contacted by cover grinding with mixed conductive LiNio , 33 Coo , 33 Mno , 33 0 2 and completely decomposed cathodically (Y. Bie et al., Chem. Commun. 2017, 53, 8324-7).
- the charging voltage should not exceed a certain level at which oxygen evolution begins.
- this voltage is around 3 - 3.5 V vs Li / Li + .
- the practical functionality of a full battery cell containing nanoparticulate lithium oxides (a mixture of L12O, L12O2 and L1O2), embedded in a matrix of Co30 4, is known (Z. Zhi, Nature Energy, 25 July 2016, 161 1 1).
- electrolytes for the anion redox battery according to the invention with nitrogen and transition metal-containing composite anode the types familiar to the person skilled in the art (liquid, gel, polymer and solid electrolytes) can be considered.
- soluble lithium salts with weakly coordinating, oxidation-stable anions are used as the conductive salt for liquid-polymer and gel-polymer systems.
- These include, for example, LiPF6, lithium fluoroalkylphosphates, LiBF 4 , imide salts (e.g. LiN (S0 2 CF 3 ) 2), UOSO2CF3, methide salts (e.g. LiC (S0 2 CF 3 ) 3), LiCI0 4 ,
- Lithium chelatoborates e.g. LiB (C 2 0 4 ) 2 , called “LiBOB”
- lithium fluorochelatoborates e.g. LiC 2 0 4 BF 2 , called “LiDFOB”
- lithium chelatophosphates e.g. LiP (C 2 0 4 ) 3, called “LiTOP”
- Li fluorochelatophosphates e.g. Li (C 2 0 4 ) 2 PF 2
- Salts with anions which are stable against anion dissociation and which are fluorine-free are particularly preferred.
- Solid electrolytes ie Li-ion-conducting glasses, ceramics or crystalline inorganic solids are also particularly preferred.
- the nitrogen and transition metal-containing composite anode materials according to the invention can be used to construct a galvanic cell according to the invention.
- they can be used either in (partially) lithium-loaded or in (partially) discharged (delithiated) form.
- delithiated anode shape is used when using a lithium-loaded cathode material, the opposite applies to the lithiated anode shape. This is explained below using a few examples:
- the anode delithiator form for example lithium imide (U2NFI), against a lithium rich cathode material, which is preferably at least one of the following compounds selected from u2o and U2O2, installed in an electrochemical cell.
- the electrochemical redox reactions then look as follows:
- a lithium-rich form of the preferred anode material for example L ⁇ MgNH or Li 4 NH
- a low-lithium form of the cathode material according to the invention for example LiOH, UO2.
- lithium peroxide can also be used, which in combination with lithium-rich anode materials can absorb additional lithium. With a medium lithium content, lithium peroxide can therefore be used both in combination with lithium-rich and low-lithium anode active materials.
- the electrochemical reactions can be formulated as follows:
- an amount of the cathode material sufficient for lithium absorption is used either in a likewise partially lithium-ionized form or as a mixture of separately present particles in lithium-loaded and discharged form.
- This procedure of balancing the electrodes is familiar to the person skilled in the art. It is also possible to accomplish the lithium required for complete lithiation in the form of a separately added lithium-rich material, for example lithium metal powder or a lithium-rich metal alloy powder (for example a Li-Si or Li-Sn alloy).
- the lithium nitrogen-containing, microcrystalline, powdered anode materials L1NH2 and L12NH were mixed in an Ar-filled glove box with a transition metal-free conductivity improver (carbon black AB 100) and PTFE powder (supplier: Aldrich) and briefly homogenized using an agate mortar.
- the weight ratios were 60% by weight of active material; 25% by weight carbon black; 15 wt% PTFE.
- the electrode material was then applied to a nickel current collector with an area of 1 cm 2 and pressed isostatically for one minute with a pressure of 10 t.
- the anode produced in this way was tested in a glass cell with a three-electrode arrangement.
- two electrodes made of lithium sheets were used as counter and reference electrodes.
- a 1 1% LiPF 6 solution in EC / DMC (1: 1) was used as the electrolyte.
- the cell with L1NH2 had a resting potential of 1300 mV, the one with L12NH had a potential of 700 mV.
- polarization was carried out with very low feed voltages up to a potential of 5 mV.
- the amount of charge consumed in each case corresponded to just under 0.1 eq of lithium.
- the polarity was then reversed and lithium removed.
- L1NH2 only about 0.3 Li could be extracted, in the case of L12NH about 0.55 Li.
- the grinding bowl was reinserted into the Ar-filled glove box and opened there.
- the ground product was separated from the grinding media by sieving.
- the grinding bowl was reinserted into the Ar-filled glove box and opened there.
- the ground product was separated from the grinding media by sieving.
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US20100129718A1 (en) | 2008-02-14 | 2010-05-27 | Hiroshi Higuchi | Negative electrode for lithium secondary battery, lithium secondary battery comprising the same, and method for producing negative electrode for lithium secondary battery |
JP2013503928A (ja) | 2009-09-02 | 2013-02-04 | ロレアル | 疎水性染料、特定の無機アルカリ剤及び/又は有機アルカリ剤、特定の化合物(i)及び特定の有機化合物(ii)を含む組成物、並びに染色におけるその使用 |
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US20130062575A1 (en) * | 2010-03-21 | 2013-03-14 | Chemetall Gmbh | Metal imide compounds as anode materials for lithium batteries and galvanic elements with a high storage capacity |
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