US20160240856A1 - Carbon Coated Electrochemically Active Powder - Google Patents
Carbon Coated Electrochemically Active Powder Download PDFInfo
- Publication number
- US20160240856A1 US20160240856A1 US15/026,016 US201415026016A US2016240856A1 US 20160240856 A1 US20160240856 A1 US 20160240856A1 US 201415026016 A US201415026016 A US 201415026016A US 2016240856 A1 US2016240856 A1 US 2016240856A1
- Authority
- US
- United States
- Prior art keywords
- powder
- sintering
- carbon
- formula
- particles
- 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.)
- Abandoned
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000000843 powder Substances 0.000 title claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 title claims description 58
- 239000002245 particle Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 26
- 150000003624 transition metals Chemical class 0.000 claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 96
- 239000000203 mixture Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 238000003991 Rietveld refinement Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910001305 LiMPO4 Inorganic materials 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 150000001457 metallic cations Chemical class 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000010793 Steam injection (oil industry) Methods 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 15
- 238000000576 coating method Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 229910001386 lithium phosphate Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 229910052493 LiFePO4 Inorganic materials 0.000 description 8
- 239000011149 active material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011236 particulate material Substances 0.000 description 8
- -1 LiFePO4 Chemical class 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002577 pseudohalo group Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910010951 LiH2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FRYDSOYOHWGSMD-UHFFFAOYSA-N [C].O Chemical class [C].O FRYDSOYOHWGSMD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002367 halogens Chemical class 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical class FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910016955 Fe1-xMnx Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- 229910013116 LiMxPO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910017033 LixM1-y Inorganic materials 0.000 description 1
- 229910017042 LixM1−y Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 239000007859 condensation product Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- VUNCWTMEJYMOOR-UHFFFAOYSA-N hexachlorocyclopentadiene Chemical compound ClC1=C(Cl)C(Cl)(Cl)C(Cl)=C1Cl VUNCWTMEJYMOOR-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 235000002908 manganese Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical group 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012713 reactive precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YTZVWGRNMGHDJE-UHFFFAOYSA-N tetralithium;silicate Chemical class [Li+].[Li+].[Li+].[Li+].[O-][Si]([O-])([O-])[O-] YTZVWGRNMGHDJE-UHFFFAOYSA-N 0.000 description 1
Images
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- 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
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
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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
- H01M4/139—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
- H01M4/366—Composites as layered products
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- 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
- 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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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 an electrochemically active powder comprising carbon-coated particles, said particles containing an electrochemically active compound, the compound preferably having an olivine or NASICON structure.
- the invention also relates to a process for manufacturing said powder and to various products containing said powder.
- the invention relates to a positive electrode comprising said powder and to a battery, in particular lithium-ion battery, containing said electrode.
- An electrochemically active powder is for instance known from US 2009/0148771 A1 wherein a lithium (Li)-based powder is disclosed.
- Said powder comprises lithium phosphate based particles, which are known for their electrochemical activity.
- said publication discloses a particulate LiM x PO 4 compound with M being among others manganese, iron, nickel and magnesium; with 0 ⁇ X ⁇ 1; and having a mean particle diameter of between 50 nm and 500 nm.
- Said particulate compound is used as active material in a cathode, wherein it is mixed with a carbon material, e.g. graphite, and with a binder.
- a known limitation of the known electrochemically active powders e.g. powders based on lithium phosphates such as LiFePO 4 , is their low conductivity, which in turn may restrict a broad application thereof.
- lithium-ion battery-driven electrical devices requiring a high rate performance of their battery may not perform up to the required intended use.
- many approaches have been applied, e.g. addition of carbon, carbon coating, metal doping, particle size control, etc.
- US 2009/0148771 A1 discloses that the addition of a particulate carbon material to a LiFePO 4 powder improves the performance of a positive battery electrode containing thereof. Said publication further demonstrates that when said carbon material contains an increased amount of graphite, better results were achieved.
- the inventors in US 2009/0148771 A1 used a ratio (I 1360 /I 1580 ) of a peak intensity (I 1360 ) at 1,360 cm ⁇ 1 to a peak intensity (I 1580 ) at 1,580 cm ⁇ 1 obtained by Raman spectrum analysis.
- the peak intensity I 1580 is attributed to the graphitized carbon
- the peak intensity I 1360 is attributed to the disordered carbon and for ratios as low as 0.25, a very good performance was achieved.
- Carbon coating is one of the most important techniques used to improve the powders' performance, in particular their conductivity, specific capacity, rate performance and cycling life.
- Various research programs showed that an effective carbon coating not only enhances the surface electronic conductivity of particulate electrochemically active materials such as lithium phosphates but it may also improve or simplify the preparation thereof.
- carbon coated LiFePO 4 can be readily prepared by milling LiFePO 4 particles with carbon powders or by in situ carbonization of organic precursors previously deposited on the surface of said LiFePO 4 particles.
- the structure of the carbon coating applied to electrochemically active particulate materials such as the above mentioned LiFePO 4 particles may significantly affect the electrochemical performance thereof.
- Carbon coatings prepared at high temperature (>800° C.) have much higher electronic conductivity than those prepared at lower temperatures ( ⁇ 600° C.).
- the cause of these benefices was the increased graphitization of the carbon coating, i.e. the presence of an increased amount of graphitized carbon in the coating to the expense of non-graphitized carbon, e.g. disordered carbon.
- the extent of graphitized carbon in a carbon based material and its ratio to the disordered carbon can be characterized as shown by US 2009/0148771 A1 by an ID/IG (disordered/graphite) peak intensity ratio as determined by Raman spectroscopy.
- ID/IG disordered/graphite
- electrochemically active particulate materials such as lithium phosphate based particles with graphitized carbon.
- Methodologies such as a) coating particles with organic precursors and using increased sintering temperatures (>800° C.) to carbonize said precursors; b) combining particles with materials having an increased amount of graphitized carbon source, e.g. carbon nanotubes, graphene, carbon nano-fibers; or c) using various catalysts, e.g. ferrocene, during sintering to achieve a higher graphitization of the carbon; were applied in attempts to enhance the properties of the electrochemically active particulate materials.
- an aim of the present invention may thus be an aim of the present invention to provide an electrochemically active particulate material such as particles containing a lithium phosphate based material, having acceptable electrochemical properties and being coated with a highly graphitized carbon layer.
- a further aim of the present invention is to provide an electrode containing a carbon-coated electrochemically active particulate material, said coating comprising a high amount of graphitized carbon, said electrode providing a battery containing thereof with optimal properties.
- the invention provides an electrochemically active powder comprising particles containing a compound represented by formula A a M m (XO 4 ) n wherein A comprises an alkaline metal; M comprises at least one transition metal and optionally at least one non-transition metal; and X is chosen among S, P and Si; wherein 0 ⁇ a ⁇ 3.2; 1 ⁇ m ⁇ 2; and 1 ⁇ n ⁇ 3; wherein said particles are at least partially coated with a layer comprising a carbonaceous material, said carbonaceous material comprising a highly ordered graphite, wherein said highly ordered graphite has a ratio (I 1360 /I 1580 ) of a peak intensity (I 1360 ) at 1360 cm ⁇ 1 to a peak intensity (I 1580 ) at 1580 cm ⁇ 1 , obtained by Raman spectrum analysis, of at most 3.05.
- FIG. 1 shows the apparatus used to manufacture the powder of the invention.
- FIG. 2 shows a temperature profile, i.e. temperature vs. time, used in a process to manufacture the powder of the invention.
- FIG. 3 shows pictographs of representative particles of the powder of the invention and those of powders used for comparison.
- the coating layer of carbonaceous material contained by the active powders of the invention had a high degree of graphitization and showed an increased uniformity. These advantageous properties may lead to an enhanced surface electronic conductivity of the active powders and to electrodes containing thereof having optimal specific capacities, enhanced rate performance and cycling life. Additional benefits of having an optimized coating may be reduced polarization effects during charge and discharge and high stability of the active powder during charge and discharge.
- the present inventors obtained a highly-graphitized and uniform carbon layer on the surface of lithium iron phosphate particles without the need of an expensive and complicated process.
- the process used to manufacture such powders utilized relatively low sintering temperature ( ⁇ 800° C.) and relatively short sintering times ( ⁇ 2 h).
- the carbon layer seems to provide the lithium iron phosphate with effective discharge capacity and rate capability.
- A is Li, Na or K.
- M is a transition metal comprising iron, manganese, vanadium, titanium, molybdenum, niobium, tungsten, zinc and mixtures thereof, said transition metals being preferably in the following oxidation states: Fe 2+ , Mn 2+ , V 2+ , V 3+ , Cr 3+ , Ti 2+ , Ti 3+ , Mo 3+ , Mo 4+ , Nb 2+ , Nb 4+ and W 4+ .
- the non-transition metal comprises magnesium and aluminum.
- the compound used in accordance with the invention has the formula LiMPO 4 , said with compound preferably having an olivine structure, where M is a metallic cation belonging to the first line of transition metals, preferably being selected from the group consisting of Mn, Fe, Co, and Ni.
- M is a combination of cations, at least one of which is selected from the group consisting of Mn, Fe, Co and Ni. More preferably M is Fe 1-x Mn x or Fe 1-x Ti x with 0 ⁇ x ⁇ 1. Most preferably M is Fe.
- the compound used in accordance with the invention has the formula Li x M 1-y M′ y (XO 4 ) n , in which 0 ⁇ X ⁇ 2; 0 ⁇ y ⁇ 0.6 and 1 ⁇ n ⁇ 1.5, wherein M is a transition metal or a mixture of transition metals from the first line of the periodic table; M′ is an element with fixed valence selected among Mg 2+ , Ca 2+ , Al 3+ , Zn 2+ or a combination of these same elements; and X is chosen from among S, P and Si, with P being preferred.
- Such compounds can be synthesized by using the precursors disclosed for example by US 2004/0033360 A1 included herein by reference.
- the compound has the formula Li x (M,M′)PO 4 , wherein 0 ⁇ x ⁇ 1, M is one or more cations selected from the group consisting of Mn, Fe, Co, Ni, and Cu, and M′ is an optional substitutional cation selected from the group consisting of Na, Mg, Ca, Ti, Zr, V, Nb, Cr, Zn, B, Al, Ga, Ge, and Sn.
- the compound is a Li-rich compound represented by formula Li 1+x M m (XO 4 ) n , wherein 0 ⁇ x ⁇ 0.2; 0 ⁇ m ⁇ 1; and 1 ⁇ n ⁇ 1.05.
- M is a transition metal, more preferably a transition metal chosen from the group consisting of iron, manganese, vanadium, titanium, molybdenum, niobium, tungsten, zinc and mixtures thereof.
- M′ is chosen from the group consisting of Mg, Ca, Sr, Ba, and B.
- M′ is Mg or B.
- X is chosen from among S, P and Si, with P being preferred.
- the Li content of the compound of this embodiment is non-stoichiometrically controlled meaning that the molar ratio Li/M is more than 1.00 and in particular for powders having a NASICON structure, preferably more than 1.5.
- the particles forming the inventive powder have a mean diameter of at least 50 nm, more preferably at least 80 nm, most preferably at least 150 nm.
- said mean diameter is at most 600 nm, more preferably at most 400 nm, most preferably at most at most 200 nm.
- the mean particle diameter of said particles is calculated from the mean value of measured longest diameters on observed images obtained, e.g., from a scanning electron microscope (SEM).
- the particles forming the inventive powder have a particle size distribution with an average particle size d50 of less than 500 nm, more preferably less than 200 nm; and preferably of more than 30 nm.
- the particle size distribution is preferably mono-modal.
- the inventive powder is characterized by a ratio (d90 ⁇ d10)/d50 of at most 1.5, more preferably of at most 1.3, most preferably at most 1.1.
- the particles forming the powder of the invention are coated with a layer comprising a carbonaceous material containing a highly ordered graphite.
- carbonaceous material is herein understood a material rich in carbon, e.g. containing carbon in an amount based on the total amount of carbonaceous material of from 60 to 100% molar, and preferably having an electronic conductivity higher than 10 ⁇ 6 S/cm at room temperature, preferably higher than 10 ⁇ 4 S/cm.
- Other elements that can be present in the carbonaceous material are hydrogen, oxygen, nitrogen, as long as they do not interfere with the chemical inertia of the carbon during the electrochemical operation.
- the ratio I 1360 /I 1580 is at most 2.80, more preferably at most 2.60, even more preferably at most 2.40, yet even more preferably at most 2.20, most preferably at most 2.10.
- the ratio I 1360 /I 1580 is at least 1.5, more preferably at least 1.8, most preferably at least 2.0.
- the amount of highly ordered graphite contained by said carbonaceous material is at least 22 wt % based on the total content of carbonaceous material, more preferably at least 28 wt %, most preferably at least 30 wt %.
- the carbonaceous material essentially consists of highly ordered graphite.
- said Li a M m (XO 4 ) n has a crystal size of at most 90 nm and preferably at most 85 nm. This is determined by Rietveld refinement of XRD data.
- the layer comprising the carbonaceous material preferably has a thickness of at least 2 nm, more preferably at least 5 nm, most preferably at least 8 nm.
- said layer has a thickness of at most 20 nm, more preferably at most 15 nm, most preferably at most 12 nm.
- said layer has a thickness of between 2 nm and 20 nm, more preferably of between 5 nm and 15 nm, most preferably of between 8 nm and 12 nm.
- the thickness of said layer can be determined using Transmission Electron Microscopy.
- the particles forming the powder of the invention have a BET of at most 25 g/m 2 , more preferably at most 20 g/m 2 , most preferably at most 18 g/m 2 .
- said BET is at least 10 g/m 2 , more preferably at least 12 g/m 2 , most preferably at least 15 g/m 2 .
- the invention relates to a carbon coated powder comprising particles containing a compound represented by formula Li 1+x FePO 4 wherein x is at least 0.01, more preferably x is at least 0.03, most preferably x is at least 0.06; wherein said particles are at least partially coated with a layer comprising a carbonaceous material; wherein said layer has a thickness of at least 3 nm, more preferably at least 6 nm, even more preferably at least 9 nm; wherein said carbonaceous material comprises a highly ordered graphite, wherein said highly ordered graphite has a ratio (I 1360 /I 1580 ) of a peak intensity (I 1360 ) at 1360 cm ⁇ 1 to a peak intensity (11580) at 1580 cm ⁇ 1 , obtained by Raman spectrum, of at least 1.50 and at most 3.00, more preferably of between 1.80 and 2.40, most preferably between 1.90 and 2.10. Most preferably said carbonaceous material essentially consists of said highly ordered graphit
- the invention also relates to a composition comprising the carbon-coated electrochemically active powder of the invention and preferably a binder, said composition being preferably used as an electrode material. Therefore, the invention also relates to an electrode material comprising the composition of the invention.
- the composition may further comprise a conductive agent, which is preferably fibrous carbon.
- the binder is preferably a material chosen from the group consisting of polyethers, polyesters, polymers based on methyl methacrylate units, acrylonitrile-based polymers, vinylidene fluorides and mixtures thereof.
- the invention further relates to an electrode comprising the electrode material of the invention.
- the invention also relates to an electrochemical cell containing at least two electrodes and at least one electrolyte, wherein at least one of the electrodes, preferably the positive electrode, is the electrode of the invention.
- cells may include cylindrical cells and prismatic cells.
- the electrolyte is a polar liquid containing one or more metallic salts in solution or a polymer, solvating or not, optionally plasticized or gelled by said polar liquid.
- the electrolyte can also be a polar liquid immobilized in a microporous separator, such as a polyolefin, a polyester, nanoparticles of silica, alumina or lithium aluminate LiAlO 2 .
- polar liquids include cyclic or linear carbonates, alkyl formiates, oligoethylene glycols, alkylethers, N-methylpyrolidinone, y-butyrolactone, tetraalakylsulfamides and mixtures thereof.
- the invention further relates to a battery containing at least one of the electrochemical cells of the invention and to various devices containing said batteries.
- devices may be portable electronic devices, e.g. portable computers, tablets, mobile phones; electrically powered vehicles; and energy storage systems.
- the invention also relates to a method for making a carbon coated electrochemically active powder, said powder comprising particles containing a compound represented by formula A a M m (XO 4 ) n wherein 0 ⁇ a ⁇ 3.2; 1 ⁇ m ⁇ 2; and 1 ⁇ n ⁇ 3; A comprises an alkaline metal; M comprises at least one transition metal and optionally at least one non-transition metal; and X is chosen among S, P and Si; preferably said powder being the inventive powder, said method comprising the steps of:
- the invention also relates to an apparatus for carrying out the inventive method.
- the inventive apparatus ( 100 ) contains a furnace ( 101 ) having a sintering chamber ( 102 ); an inlet ( 103 ) to introduce an inert gas in said sintering chamber; a steam source ( 104 ) used to produce steam and means ( 105 ) to transport the steam and inject it into the sintering chamber ( 102 ).
- the furnace can also comprise an outlet ( 106 ) used to evacuate the steam in excess.
- the sources of the elements utilized therein are mixed together and said mixture is subjected to further processing.
- step i. with step ii. of the inventive method, e.g. mixing said sources of elements during heating up, it is preferred that said sources of elements are mixed before the commencing of step ii.
- the mixture obtained at step i. of the inventive method is preferably a homogeneous mixture, i.e. a mixture having an essentially uniform composition throughout.
- Homogeneous mixtures can be obtained for example by mixing said sources of elements in a ball mill, or by using horizontal or vertical attritors, rotor-stator machines, high-energy mills, planetary kneaders, shaking apparatuses or shaking tables, ultrasonic apparatuses or high shear mixers or combinations of the abovementioned apparatuses.
- the precursors are in the form of powders, preferably having a sub-micron size distribution, more preferably having a sub-micron d50 size distribution.
- A is lithium and the source of lithium is preferably a compound selected from the group consisting of lithium oxide, lithium hydroxide, lithium carbonate, neutral phosphate Li 3 PO 4 , acid phosphate LiH 2 PO 4 , lithium orthosilicates, lithium metasilicates, lithium polysilicates, lithium sulfate, lithium oxalate, lithium acetate, and mixtures thereof.
- the source of M is a compound comprising a transition metal or mixture of transition metals selected from the group consisting of iron, manganese, cobalt, nickel, vanadium, titanium, chromium, and copper.
- the source of M is a compound selected from the group consisting of iron (III) oxide, magnetite, manganese dioxide, di-vanadimn pentoxide, trivalent iron phosphate, trivalent iron nitrate, trivalent iron sulfate, iron hydroxyphosphate, lithium hydroxyphosphate, trivalent iron sulfate, trivalent iron nitrate, and mixtures thereof.
- the source of M is a mixture of an iron-containing precursor and an M′-containing precursor.
- suitable iron containing precursors include iron (II) phosphate, iron (II) oxalate and iron (II) oxide.
- suitable M′-containing precursors include at least one compound containing Mg and B such as an oxide, hydroxide or organic complex.
- the source of X is selected from the group consisting of sulfuric acid, lithium sulfate, phosphoric acid, phosphoric acid esters, neutral phosphate Li 3 PO 4 , acid phosphate LiH 2 PO 4 , monoanunonium phosphate, diarmnonium phosphate, trivalent iron phosphate, manganese and ammonium phosphate (NH 4 MnPO 4 ), silica, lithium silicates, alkoxysilanes and partial hydrolysis products thereof, and mixtures thereof.
- the source of X is a metal sulfate, e.g. trivalent iron phosphate.
- the source of M is also the source of X
- the source of A is also the source of X
- the source of lithium is also the source of X
- the source of X is also the source of lithium
- the source of carbon is an organic precursor material or a combination of organic precursor materials.
- any organic precursor material or combination of organic precursor materials leading to the carbonaceous material with the desired property is suitable for utilization in accordance with the present invention.
- said precursors do not affect the stability of the particulate material.
- Preferred precursors that can be suitably utilized as the carbon source in accordance with the invention include, but are not limited to: hydrocarbons and their derivatives, especially those comprising polycyclic aromatic moieties, like pitch and tar derivatives, perylene and its derivatives; polyhydric compounds like sugars and carbon hydrates and their derivatives; and polymers.
- Preferred examples of such polymers include polyolefins, polybutadienes, polyvinylic alcohol, phenol condensation products, including those from a reaction with an aldehyde, polymers derived from furfurylic alcohol, polymers derivatives of styrene, divinylbenzene, naphtalene, perylene, acrylonitrile, vinyl acetate; cellulose, starch and their esters and ethers, and mixtures thereof.
- Y represents a halogen or a pseudo-halogen.
- pseudo-halogen means an organic or inorganic radical susceptible of existing in the form of an ion Y ⁇ and which can form a corresponding protonated compound HY.
- halogen and pseudo-halogen include F, Cl, Br, I, CN, SCN, CNO, OH, N 3 , RCO 2 , RSO 3 wherein R is H or an organic radical.
- the formation by reduction of CY bonds is preferably performed in the presence of reducing elements such as hydrogen, zinc, magnesium, Ti 3+ ions, T 2+ ions, Sm 2+ ions, Cr 2+ ions, V 2+ ions, tetrakis(dialkylamino ethylene) or phosphines.
- reducing elements such as hydrogen, zinc, magnesium, Ti 3+ ions, T 2+ ions, Sm 2+ ions, Cr 2+ ions, V 2+ ions, tetrakis(dialkylamino ethylene) or phosphines.
- reducing elements such as hydrogen, zinc, magnesium, Ti 3+ ions, T 2+ ions, Sm 2+ ions, Cr 2+ ions, V 2+ ions, tetrakis(dialkylamino ethylene) or phosphines.
- Palladium or nickel derivatives are particularly efficient, particularly in the form of complexes with phosphorous or nitrogen compounds like 2,2′-bipyridine.
- Compounds susceptible of generating carbon by reduction include perhalocarbons, particularly in the form of polymers, hexachlorobutadiene and hexachlorocyclopentadiene.
- Another way to obtain a carbonaceous material comprises the elimination of the hydrogenated compound HY, Y being as defined above, according to the equation:
- Compounds susceptible of generating carbon from reduction include organic compounds comprising an even number of hydrogen atoms and Y groups, such as hydrohalocarbons, in particular in the form of polymers, such as vinylidene polyfluoride, polychloride or polybromide, or carbon hydrates.
- the dehydro (pseudo) halogenation can be obtained at low temperature, including room temperature, by reacting a base with the HY compound to form a salt.
- Suitable bases include tertiary basis, amines, amidines, guanidines, imidazoles, inorganic bases such as alkaline hydroxides, organometallic compounds behaving like strong bases, such as A(N(Si(CH 3 ) 3 ) 2 , LiN[CH(CH 3 ) 2 ] 2 , and butyl-lithium.
- the following compounds are used as sources to prepare a carbon-coated lithium-rich lithium iron phosphate Li 1+x FePO 4 with 0 ⁇ x ⁇ 0.2: Li 3 PO 4 as the source for Li and P, Fe 3 (PO 4 ) 2 .8H 2 O as the source for Fe and P, and cellulose for carbon, wherein the Li: Fe molar ratio was 1.06:1 and the weight ratio of carbon source was 5.85 wt % (defined as m Cellulose /m Li3PO4 +m Fe3(PO4)2.8H2O ).
- precursors For convenience, the sources of the elements utilized in accordance with the present invention are hereinafter called precursors.
- the mixture of precursors i.e. the mixture containing the sources of the elements utilized in the present invention
- a heating rate 203
- a temperature 204
- the sintering temperature is preferably at least 500° C., more preferably at least 550° C., most preferably at least 600° C.
- the sintering temperature is at most 800° C., more preferably at most 750° C., most preferably at most 700° C.
- the sintering temperature is between 500° C.
- the sintering temperature can be constant during the sintering process or it can vary. In case the sintering temperature varies during the sintering process, by sintering temperature in herein understood the average of the variations. The sintering temperature is considered as the temperature of the sintering chamber as measured with typical means utilized to read such high temperatures.
- said mixture is heat up with a heating rate ( 203 ) of at least 3° C./min, more preferably of at least 5° C./min, most preferably of at least 6° C./min.
- said mixture is heat up with a heating rate of at most 15° C./min, more preferably of at most 10° C./min, most preferably of at most 8° C./min.
- said heating rate is between 3° C./min and 15° C./min, more preferably between 5° C./min and 10° C./min, most preferably between 6° C./min and 8° C./min.
- the time used for sintering (206), hereinafter referred to as the sintering time, is preferably at least 60 min, more preferably at least 80 min, most preferably at least 100 min.
- Said sintering time is preferably at most 600 min, more preferably at most 300 min, most preferably at most 180 min.
- Said sintering time is preferably between 60 and 600 min, more preferably between 80 and 300 min, most preferably between 100 and 180 min.
- steam is continuously injected in the sintering chamber before, during and/or after said heating up and/or said sintering of said mixture, for an injection time.
- continuous injection is herein understood that fresh steam is continuously supplied to the sintering chamber throughout the injection time.
- a first steam-injection is carried out during the heating-up step for a first injection time and a second steam-injection is carried out during the sintering step for a second injection time.
- a steam-injection is commenced during the heating-up step ( 207 ) and extended uninterruptedly to the sintering step wherein said steam-injection during sintering is carried out for at least part ( 208 ) of said sintering step.
- the time for which steam is injected is shown by the shaded area ( 209 ). It is also possible to commence the steam-injection before or during the heating up, sintering and/or cooling step.
- the steam is continuously injected in the sintering chamber during heating up said mixture of precursors to the sintering temperature.
- the steam injection commences ( 204 ) during said heating up when the temperature in the sintering chamber is at least a fifth of the sintering temperature, more preferably at least a third of the sintering temperature.
- the steam injection preferably commences during said heating up when the temperature in the sintering chamber is at least 150° C., more preferably at least 200° C., most preferably at least 250° C.
- the steam injection commences when the temperature in the sintering chamber is substantially equal with the sintering temperature ( 202 ).
- the steam injection commences ( 207 ) when the temperature in the sintering chamber is below the sintering temperature but preferably at least a fifth of said sintering temperature and the steam injection is extended uninterruptedly to the sintering step; wherein said steam-injection during sintering is carried out for least part of said sintering step; wherein the steam injection during the sintering step is carried out for an injection time of at most 1 ⁇ 4 of the total sintering time, more preferably of at most 1 ⁇ 2 of the total sintering time, most preferably of at most 1 ⁇ 4 of the total sintering time.
- the steam injection during the sintering step is carried out for an injection time of at least 1/10, more preferably of at least 1 ⁇ 5 of the total sintering time.
- the steam injection is uninterruptedly carried out during a total injection time of at least about 1 ⁇ 4 of the time needed to both heat up and sinter said mixture of precursors, more preferably of at least about 1 ⁇ 3, most preferably of at least about 1 ⁇ 2.
- said steam injection is carried out uninterruptedly during at least part of the heating up step and at least part of the sintering step.
- the steam injection is extended to the sintering step, i.e. there is no discontinuity in steam injection between the heating up step and sintering step.
- the steam is injected into the sintering chamber during an injection time, which can vary from seconds to hours.
- the injection time during the heating up step is at least 25% of the total time needed to heat up said mixture of precursors to the sintering temperature, more preferably at least 50%, most preferably at least 75%.
- the injection time during the sintering step is at least 10% of the total sintering time, more preferably at least 15%, even more preferably at least 20%, most preferably at least 75%.
- the injection time during the heating up step is at least 25% of the total time needed to heat up said mixture of precursors to the sintering temperature, more preferably at least 50%, most preferably at least 75% and the injection time during the sintering step is at least 10% of the total sintering time, more preferably at least 15%, even more preferably at least 20%, most preferably at least 75% and there is no discontinuity in the steam injection between the heating up step and sintering step.
- steam is injected in the sintering chamber during a part, preferably the initial part, of the sintering step, the remaining part, preferably the last part, of the sintering step being carried out in a steam-free atmosphere.
- the steam is preferably injected at atmospheric pressure in the sintering chamber and is preferably water-based, i.e. water is mainly used as the liquid medium used to produce the steam.
- the steam is at a temperature of at least 150° C., more preferably at least 200° C., most preferably at least 250° C.
- the temperature of the steam can be increased for example by mixing the water-based steam with flammable gases and igniting said gases thereby transferring heat to the steam. It is particularly advantageous to use a water-based steam and allow water to react with the precursors since better results are obtained.
- the steam injection such that an amount of at least 1.5 L of water per 150 g of active material participate are reacted, more preferably at least 2.0 L. most preferably at least 2.5 L.
- said amount of reacted water is at most 1.5 L, more preferably at most 2.0 L, most preferably at most 2.5 L.
- the amount of reacted water can be calculated from the difference between the amount of water introduced as steam and the amount of water captured at the end of the method of the invention.
- the steam can be supplied to and injected in the sintering chamber from a steam source via suitable piping for example. Any conventional steam sources using conventional materials and conventional steam producing methods can be used in accordance with the invention.
- the steam can also be collected from the sintering chamber and condensed to recover the liquid medium used to produce said steam, e.g. water.
- the steam is injected with a flow rate of at least 10 L/min, more preferably at least 20 L/min, most preferably at least 25 L/min.
- the steam is injected with a flow rate of at most 50 L/min, more preferably at most 40 L/min, most preferably at most 30 L/min.
- sintering chamber By sintering chamber is herein understood the chamber wherein the heating up and sintering of the mixture of precursors takes place.
- injecting steam in the sintering chamber By injecting steam in the sintering chamber is herein understood that an atmosphere containing steam is provided in said sintering chamber.
- the sintering chamber is provided with a stream of an inert gas.
- gases include nitrogen, carbon dioxide, or noble gases such as helium or argon, or mixtures thereof.
- inert gas said gas may also contain small amounts of reactive gases, e.g. hydrogen.
- the inert gas is a mixture containing a small amount of a reactive gas, preferably hydrogen, and an inert gas with a majority of said inert gas; preferably in a volume ratio inert gas/H 2 of 99 to 95:1 to 5 v/v, wherein the another inert gas is preferably nitrogen.
- the inert gas is used to blanket the reactive precursors used in accordance with the invention to prevent unwanted reactions from taking place.
- the stream of inert gas is provided to the sintering chamber throughout the entire process of preparing the powders of the invention.
- the cooling rate ( 210 ) is preferably at least 1° C./min, more preferably of at least 2° C./min, most preferably of at least 4° C./min.
- said cooling rate of at most 10° C./min, more preferably of at most 7° C./min, most preferably of at most 5° C./min.
- said cooling rate is between 1° C./min and 10° C./min, more preferably between 2° C./min and 7° C./min, most preferably between 4° C./min and 5° C./min.
- the Li:Fe ratio in the blend was 1.06:1.
- the ratio M Cellulose /(M Li3PO4 +M Fe3(PO4)2.8H2O ) was 5.85 wt %.
- the blend was transferred into a furnace provided with an inlet for steam injection and provided with a stream of an inert gas composed of N 2 /H 2 (99:1, v/v).
- the blend was heated up to a sintering temperature of 600′C and sintered at that temperature for 2 h.
- the heating up rate was 5° C./min.
- Steam injection into the furnace commenced during the heating up of said furnace when the temperature in the furnace reached 250° C. and it was extended uninterrupted to the sintering step.
- the total steam injection time was 100 minutes.
- the total sintering time in the presence of steam amounted to 0.5 h.
- the temperature profile and an indication of when steam injection is carried out are shown in FIG. 2 .
- Example 1 The process of Example 1 was repeated without using steam injection.
- FIG. 3 shows Transmission Electron Microscopy (TEM) pictographs of the powders of Ex. 1 ( 300 ) and C. Exp. 1 ( 400 ) and 2 ( 500 ), respectively.
- the powder of Ex 1 contains particles ( 301 ) coated with a carbon coating layer ( 302 ) having a thickness of around 10 nm, whereas the carbon coatings ( 402 and 502 ) on the particles ( 401 and 501 ) forming the powders of the Comparative Experiments have a thickness of maximum about 3 nm.
- Table 1 further shows the peak-intensity ratio I 1360 /I 1580 as obtained by Raman Spectroscopy of the obtained powders.
- the ratio I 1360 /I 1580 is an indication of the extent of carbon's graphitization. The lower the ratio I 1360 /I 1580 , the higher the extent of graphitization, i.e. the amount of highly ordered graphite in the carbon layer. Example 1 shows the lowest ratio I 1360 /I 1580 indicating that the carbon layer has a high amount of highly ordered graphite.
- a slurry was prepared by mixing the obtained powders with 10 wt % carbon black and 10 wt % PVDF into N-Methyl Pyrrolidone (NMP) and deposited on an Al foil as current collector.
- NMP N-Methyl Pyrrolidone
- the obtained electrode containing 80 wt % active material was used as the positive electrode in the manufacturing of the coin cells, using a loading of 6 mg/cm 2 active material.
- the negative electrodes were made of metallic Li.
- the coin cells were cycled in LiBF 4 based electrolyte between 2.5 and 4 0 V at various C-rates.
- Example 1 shows the highest charge capacity (CQ1), highest discharge capacity (DQ1) and best rate capabilities in all C-rate tests even at a high rate as 20 C
- Table 3 shows the crystal sizes, obtained by the Rietveld method, of the powders.
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Abstract
Description
- The invention relates to an electrochemically active powder comprising carbon-coated particles, said particles containing an electrochemically active compound, the compound preferably having an olivine or NASICON structure. The invention also relates to a process for manufacturing said powder and to various products containing said powder. In particular the invention relates to a positive electrode comprising said powder and to a battery, in particular lithium-ion battery, containing said electrode.
- An electrochemically active powder is for instance known from US 2009/0148771 A1 wherein a lithium (Li)-based powder is disclosed. Said powder comprises lithium phosphate based particles, which are known for their electrochemical activity. In particular, said publication discloses a particulate LiMxPO4 compound with M being among others manganese, iron, nickel and magnesium; with 0≦X≦1; and having a mean particle diameter of between 50 nm and 500 nm. Said particulate compound is used as active material in a cathode, wherein it is mixed with a carbon material, e.g. graphite, and with a binder.
- A known limitation of the known electrochemically active powders, e.g. powders based on lithium phosphates such as LiFePO4, is their low conductivity, which in turn may restrict a broad application thereof. In particular lithium-ion battery-driven electrical devices requiring a high rate performance of their battery may not perform up to the required intended use. In order to improve the conductivity and achieve better electrochemical performance of such materials, many approaches have been applied, e.g. addition of carbon, carbon coating, metal doping, particle size control, etc.
- For example, US 2009/0148771 A1 discloses that the addition of a particulate carbon material to a LiFePO4 powder improves the performance of a positive battery electrode containing thereof. Said publication further demonstrates that when said carbon material contains an increased amount of graphite, better results were achieved. To quantify the amount of graphite in the particulate carbon material, the inventors in US 2009/0148771 A1 used a ratio (I1360/I1580) of a peak intensity (I1360) at 1,360 cm−1 to a peak intensity (I1580) at 1,580 cm−1 obtained by Raman spectrum analysis. As explained therein, the peak intensity I1580 is attributed to the graphitized carbon, whereas the peak intensity I1360 is attributed to the disordered carbon and for ratios as low as 0.25, a very good performance was achieved.
- However, another optimal way to improve the conductivity of known electrochemically active powders and in particular of those powders based on lithium phosphates such as LiFePO4, is to cover the particles of the powders with a carbon coating.
- Carbon coating is one of the most important techniques used to improve the powders' performance, in particular their conductivity, specific capacity, rate performance and cycling life. Various research programs showed that an effective carbon coating not only enhances the surface electronic conductivity of particulate electrochemically active materials such as lithium phosphates but it may also improve or simplify the preparation thereof. For instance, carbon coated LiFePO4 can be readily prepared by milling LiFePO4 particles with carbon powders or by in situ carbonization of organic precursors previously deposited on the surface of said LiFePO4 particles.
- However, the structure of the carbon coating applied to electrochemically active particulate materials such as the above mentioned LiFePO4 particles, may significantly affect the electrochemical performance thereof. Carbon coatings prepared at high temperature (>800° C.) have much higher electronic conductivity than those prepared at lower temperatures (<600° C.). Supposedly, the cause of these benefices was the increased graphitization of the carbon coating, i.e. the presence of an increased amount of graphitized carbon in the coating to the expense of non-graphitized carbon, e.g. disordered carbon. The extent of graphitized carbon in a carbon based material and its ratio to the disordered carbon can be characterized as shown by US 2009/0148771 A1 by an ID/IG (disordered/graphite) peak intensity ratio as determined by Raman spectroscopy. The lower the ID/IG ratio, the higher the amount of graphitized carbon.
- As a consequence of such insights, various attempts were made to coat electrochemically active particulate materials such as lithium phosphate based particles with graphitized carbon. Methodologies such as a) coating particles with organic precursors and using increased sintering temperatures (>800° C.) to carbonize said precursors; b) combining particles with materials having an increased amount of graphitized carbon source, e.g. carbon nanotubes, graphene, carbon nano-fibers; or c) using various catalysts, e.g. ferrocene, during sintering to achieve a higher graphitization of the carbon; were applied in attempts to enhance the properties of the electrochemically active particulate materials.
- However, all the above enumerated approaches have disadvantages and none succeeded in achieving an optimal product. For instances, higher sintering temperatures not only that could result in particle agglomeration of the electrochemically active particulate materials such as lithium phosphate based particles but usually lead to an oxidation of said materials which in turn may strongly decrease their electrochemical activity. In other words, although obtaining particles coated with an acceptably graphitized carbon layer, during the sintering process, the electrochemically activity of the obtained powders is reduced below an acceptable level.
- On the other hand, by reducing the sintering temperatures in an attempt to avoid its deleterious effects on the electrochemical activity of the active particulate materials, dissatisfactory carbon layers with insufficient amounts of graphitized carbon are achieved.
- It may thus be an aim of the present invention to provide an electrochemically active particulate material such as particles containing a lithium phosphate based material, having acceptable electrochemical properties and being coated with a highly graphitized carbon layer. A further aim of the present invention is to provide an electrode containing a carbon-coated electrochemically active particulate material, said coating comprising a high amount of graphitized carbon, said electrode providing a battery containing thereof with optimal properties.
- The invention provides an electrochemically active powder comprising particles containing a compound represented by formula AaMm(XO4)n wherein A comprises an alkaline metal; M comprises at least one transition metal and optionally at least one non-transition metal; and X is chosen among S, P and Si; wherein 0≦a≦3.2; 1≦m≦2; and 1≦n≦3; wherein said particles are at least partially coated with a layer comprising a carbonaceous material, said carbonaceous material comprising a highly ordered graphite, wherein said highly ordered graphite has a ratio (I1360/I1580) of a peak intensity (I1360) at 1360 cm−1 to a peak intensity (I1580) at 1580 cm−1, obtained by Raman spectrum analysis, of at most 3.05.
- Hereinafter the figures are explained:
-
FIG. 1 shows the apparatus used to manufacture the powder of the invention. -
FIG. 2 shows a temperature profile, i.e. temperature vs. time, used in a process to manufacture the powder of the invention. -
FIG. 3 shows pictographs of representative particles of the powder of the invention and those of powders used for comparison. - The present inventors surprisingly observed that the coating layer of carbonaceous material contained by the active powders of the invention had a high degree of graphitization and showed an increased uniformity. These advantageous properties may lead to an enhanced surface electronic conductivity of the active powders and to electrodes containing thereof having optimal specific capacities, enhanced rate performance and cycling life. Additional benefits of having an optimized coating may be reduced polarization effects during charge and discharge and high stability of the active powder during charge and discharge.
- In particular the present inventors obtained a highly-graphitized and uniform carbon layer on the surface of lithium iron phosphate particles without the need of an expensive and complicated process. The process used to manufacture such powders, utilized relatively low sintering temperature (<800° C.) and relatively short sintering times (≦2 h). The carbon layer seems to provide the lithium iron phosphate with effective discharge capacity and rate capability.
- In the compound used as active materials according to the present invention, preferably A is Li, Na or K. Preferably, M is a transition metal comprising iron, manganese, vanadium, titanium, molybdenum, niobium, tungsten, zinc and mixtures thereof, said transition metals being preferably in the following oxidation states: Fe2+, Mn2+, V2+, V3+, Cr3+, Ti2+, Ti3+, Mo3+, Mo4+, Nb2+, Nb4+ and W4+. Preferably, the non-transition metal comprises magnesium and aluminum.
- In a first embodiment, the compound used in accordance with the invention has the formula LiMPO4, said with compound preferably having an olivine structure, where M is a metallic cation belonging to the first line of transition metals, preferably being selected from the group consisting of Mn, Fe, Co, and Ni. Such compounds can be synthesized by using the precursors disclosed for example by U.S. Pat. No. 5,910,382 included herein by reference. Preferably, M is a combination of cations, at least one of which is selected from the group consisting of Mn, Fe, Co and Ni. More preferably M is Fe1-xMnx or Fe1-xTix with 0<x<1. Most preferably M is Fe.
- In a second embodiment, the compound used in accordance with the invention has the formula LixM1-yM′y(XO4)n, in which 0≦X≦2; 0≦y≦0.6 and 1≦n≦1.5, wherein M is a transition metal or a mixture of transition metals from the first line of the periodic table; M′ is an element with fixed valence selected among Mg2+, Ca2+, Al3+, Zn2+ or a combination of these same elements; and X is chosen from among S, P and Si, with P being preferred. Such compounds can be synthesized by using the precursors disclosed for example by US 2004/0033360 A1 included herein by reference.
- In a third embodiment of the invention, the compound has the formula Lix(M,M′)PO4, wherein 0≦x≦1, M is one or more cations selected from the group consisting of Mn, Fe, Co, Ni, and Cu, and M′ is an optional substitutional cation selected from the group consisting of Na, Mg, Ca, Ti, Zr, V, Nb, Cr, Zn, B, Al, Ga, Ge, and Sn.
- In a fourth preferred embodiment of the invention, the compound has the formula LiuMv(XO4)w with u=1, 2 or 3; v=1 or 2; w=1 or 3; M has a formula TiaVbCrcMndFeeCofNigSchNbi with a+b+c+d+e+f+g+h+i=1 and X is Px-1Sx with 0≦x≦1.
- In a preferred embodiment, the compound is a Li-rich compound represented by formula Li1+xMm(XO4)n, wherein 0<x≦0.2; 0≦m≦1; and 1≦n≦1.05. Preferably 0<x≦0.2; 0≦m≦1; and n=1. Preferably, M is a transition metal, more preferably a transition metal chosen from the group consisting of iron, manganese, vanadium, titanium, molybdenum, niobium, tungsten, zinc and mixtures thereof. Alternatively M has the formula M=Fe1-mM′m, with 0≦m≦0.025, wherein M′ is either one or more elements chosen from the group consisting of alkaline earth metals and non-metals. Preferably M′ is chosen from the group consisting of Mg, Ca, Sr, Ba, and B. Most preferably, M′ is Mg or B. Preferably, X is chosen from among S, P and Si, with P being preferred. The Li content of the compound of this embodiment is non-stoichiometrically controlled meaning that the molar ratio Li/M is more than 1.00 and in particular for powders having a NASICON structure, preferably more than 1.5.
- Preferably, the particles forming the inventive powder have a mean diameter of at least 50 nm, more preferably at least 80 nm, most preferably at least 150 nm. Preferably, said mean diameter is at most 600 nm, more preferably at most 400 nm, most preferably at most at most 200 nm. The mean particle diameter of said particles is calculated from the mean value of measured longest diameters on observed images obtained, e.g., from a scanning electron microscope (SEM).
- Preferably, the particles forming the inventive powder have a particle size distribution with an average particle size d50 of less than 500 nm, more preferably less than 200 nm; and preferably of more than 30 nm. The particle size distribution is preferably mono-modal. Preferably, the inventive powder is characterized by a ratio (d90−d10)/d50 of at most 1.5, more preferably of at most 1.3, most preferably at most 1.1.
- In accordance to the invention, the particles forming the powder of the invention are coated with a layer comprising a carbonaceous material containing a highly ordered graphite. By carbonaceous material is herein understood a material rich in carbon, e.g. containing carbon in an amount based on the total amount of carbonaceous material of from 60 to 100% molar, and preferably having an electronic conductivity higher than 10−6 S/cm at room temperature, preferably higher than 10−4 S/cm. Other elements that can be present in the carbonaceous material are hydrogen, oxygen, nitrogen, as long as they do not interfere with the chemical inertia of the carbon during the electrochemical operation. By highly ordered graphite is herein understood a graphite having a ratio (I1360/I1580) of a peak intensity (I1360) at 1360 cm−1 to a peak intensity (I1580) at 1580 cm−1, obtained by Raman spectrum analysis, of at most 3.0 5. Preferably, the ratio I1360/I1580 is at most 2.80, more preferably at most 2.60, even more preferably at most 2.40, yet even more preferably at most 2.20, most preferably at most 2.10. Preferably, the ratio I1360/I1580 is at least 1.5, more preferably at least 1.8, most preferably at least 2.0. Preferably, the amount of highly ordered graphite contained by said carbonaceous material is at least 22 wt % based on the total content of carbonaceous material, more preferably at least 28 wt %, most preferably at least 30 wt %. In a preferred embodiment, the carbonaceous material essentially consists of highly ordered graphite.
- Preferably, said LiaMm(XO4)n has a crystal size of at most 90 nm and preferably at most 85 nm. This is determined by Rietveld refinement of XRD data.
- Thanks to the relatively low sintering temperatures and periods used in the disclosed method, a small crystal size combined with a relatively high degree of graphitization can be obtained, whereas in prior art methods the crystal size will grow to around 100 nm or even above if a sintering temperature and period allowing sufficient graphitization is chosen.
- The layer comprising the carbonaceous material preferably has a thickness of at least 2 nm, more preferably at least 5 nm, most preferably at least 8 nm. Preferably, said layer has a thickness of at most 20 nm, more preferably at most 15 nm, most preferably at most 12 nm. Preferably, said layer has a thickness of between 2 nm and 20 nm, more preferably of between 5 nm and 15 nm, most preferably of between 8 nm and 12 nm. The thickness of said layer can be determined using Transmission Electron Microscopy.
- Preferably, the particles forming the powder of the invention have a BET of at most 25 g/m2, more preferably at most 20 g/m2, most preferably at most 18 g/m2. Preferably, said BET is at least 10 g/m2, more preferably at least 12 g/m2, most preferably at least 15 g/m2.
- In a preferred embodiment, the invention relates to a carbon coated powder comprising particles containing a compound represented by formula Li1+xFePO4 wherein x is at least 0.01, more preferably x is at least 0.03, most preferably x is at least 0.06; wherein said particles are at least partially coated with a layer comprising a carbonaceous material; wherein said layer has a thickness of at least 3 nm, more preferably at least 6 nm, even more preferably at least 9 nm; wherein said carbonaceous material comprises a highly ordered graphite, wherein said highly ordered graphite has a ratio (I1360/I1580) of a peak intensity (I1360) at 1360 cm−1 to a peak intensity (11580) at 1580 cm−1, obtained by Raman spectrum, of at least 1.50 and at most 3.00, more preferably of between 1.80 and 2.40, most preferably between 1.90 and 2.10. Most preferably said carbonaceous material essentially consists of said highly ordered graphite. Most preferably the thickness of said layer is between 8 nm and 12 nm.
- The invention also relates to a composition comprising the carbon-coated electrochemically active powder of the invention and preferably a binder, said composition being preferably used as an electrode material. Therefore, the invention also relates to an electrode material comprising the composition of the invention. The composition may further comprise a conductive agent, which is preferably fibrous carbon. The binder is preferably a material chosen from the group consisting of polyethers, polyesters, polymers based on methyl methacrylate units, acrylonitrile-based polymers, vinylidene fluorides and mixtures thereof. The invention further relates to an electrode comprising the electrode material of the invention.
- The invention also relates to an electrochemical cell containing at least two electrodes and at least one electrolyte, wherein at least one of the electrodes, preferably the positive electrode, is the electrode of the invention. Examples of cells may include cylindrical cells and prismatic cells. Preferably, the electrolyte is a polar liquid containing one or more metallic salts in solution or a polymer, solvating or not, optionally plasticized or gelled by said polar liquid. The electrolyte can also be a polar liquid immobilized in a microporous separator, such as a polyolefin, a polyester, nanoparticles of silica, alumina or lithium aluminate LiAlO2. Examples of polar liquids include cyclic or linear carbonates, alkyl formiates, oligoethylene glycols, alkylethers, N-methylpyrolidinone, y-butyrolactone, tetraalakylsulfamides and mixtures thereof.
- The invention further relates to a battery containing at least one of the electrochemical cells of the invention and to various devices containing said batteries. Examples of devices may be portable electronic devices, e.g. portable computers, tablets, mobile phones; electrically powered vehicles; and energy storage systems.
- The invention also relates to a method for making a carbon coated electrochemically active powder, said powder comprising particles containing a compound represented by formula AaMm(XO4)n wherein 0<a≦3.2; 1≦m≦2; and 1≦n≦3; A comprises an alkaline metal; M comprises at least one transition metal and optionally at least one non-transition metal; and X is chosen among S, P and Si; preferably said powder being the inventive powder, said method comprising the steps of:
-
- i. providing a mixture of the following precursors:
- a. a source of an element A;
- b. a source of an element M;
- c. a source of an element X; and
- d. a source of carbon;
- wherein the sources of elements A, M and X are introduced in whole or in part in the form of compounds having the at least one source element;
- ii. heating up said mixture in a sintering chamber to a sintering temperature of at least 500° C. and sintering said mixture at said sintering temperature for a first period of time, wherein a stream of inert gas is provided to said chamber;
- iii. continuously injecting steam in said sintering chamber before, during and/or after said heating up and/or said sintering of said mixture, for an injection time; thereby producing particles containing said compound wherein the particles are at least partially coated with a carbonaceous material containing a highly graphitized carbon; and
- iv. cooling said powder to preferably room temperature.
- i. providing a mixture of the following precursors:
- The invention also relates to an apparatus for carrying out the inventive method. With reference to
FIG. 1 , the inventive apparatus (100) contains a furnace (101) having a sintering chamber (102); an inlet (103) to introduce an inert gas in said sintering chamber; a steam source (104) used to produce steam and means (105) to transport the steam and inject it into the sintering chamber (102). The furnace can also comprise an outlet (106) used to evacuate the steam in excess. - In accordance with the invention, the sources of the elements utilized therein are mixed together and said mixture is subjected to further processing. Although it is also possible to combine step i. with step ii. of the inventive method, e.g. mixing said sources of elements during heating up, it is preferred that said sources of elements are mixed before the commencing of step ii. The mixture obtained at step i. of the inventive method is preferably a homogeneous mixture, i.e. a mixture having an essentially uniform composition throughout. Homogeneous mixtures can be obtained for example by mixing said sources of elements in a ball mill, or by using horizontal or vertical attritors, rotor-stator machines, high-energy mills, planetary kneaders, shaking apparatuses or shaking tables, ultrasonic apparatuses or high shear mixers or combinations of the abovementioned apparatuses. To achieve homogeneous mixtures, preferably the precursors are in the form of powders, preferably having a sub-micron size distribution, more preferably having a sub-micron d50 size distribution.
- In a preferred embodiment of the inventive method, A is lithium and the source of lithium is preferably a compound selected from the group consisting of lithium oxide, lithium hydroxide, lithium carbonate, neutral phosphate Li3PO4, acid phosphate LiH2PO4, lithium orthosilicates, lithium metasilicates, lithium polysilicates, lithium sulfate, lithium oxalate, lithium acetate, and mixtures thereof.
- Preferably, the source of M is a compound comprising a transition metal or mixture of transition metals selected from the group consisting of iron, manganese, cobalt, nickel, vanadium, titanium, chromium, and copper. In a preferred embodiment, the source of M is a compound selected from the group consisting of iron (III) oxide, magnetite, manganese dioxide, di-vanadimn pentoxide, trivalent iron phosphate, trivalent iron nitrate, trivalent iron sulfate, iron hydroxyphosphate, lithium hydroxyphosphate, trivalent iron sulfate, trivalent iron nitrate, and mixtures thereof. Preferably, the source of M is a mixture of an iron-containing precursor and an M′-containing precursor. Examples of suitable iron containing precursors include iron (II) phosphate, iron (II) oxalate and iron (II) oxide. Examples of suitable M′-containing precursors include at least one compound containing Mg and B such as an oxide, hydroxide or organic complex.
- Preferably, the source of X is selected from the group consisting of sulfuric acid, lithium sulfate, phosphoric acid, phosphoric acid esters, neutral phosphate Li3PO4, acid phosphate LiH2PO4, monoanunonium phosphate, diarmnonium phosphate, trivalent iron phosphate, manganese and ammonium phosphate (NH4MnPO4), silica, lithium silicates, alkoxysilanes and partial hydrolysis products thereof, and mixtures thereof. In a preferred embodiment, the source of X is a metal sulfate, e.g. trivalent iron phosphate.
- It is also possible in accordance with the invention that the source of M is also the source of X, the source of A is also the source of X; or when A is lithium, the source of lithium is also the source of X, or the source of X is also the source of lithium.
- Preferably, the source of carbon is an organic precursor material or a combination of organic precursor materials. In general, any organic precursor material or combination of organic precursor materials leading to the carbonaceous material with the desired property is suitable for utilization in accordance with the present invention. Preferably, said precursors do not affect the stability of the particulate material.
- Preferred precursors that can be suitably utilized as the carbon source in accordance with the invention include, but are not limited to: hydrocarbons and their derivatives, especially those comprising polycyclic aromatic moieties, like pitch and tar derivatives, perylene and its derivatives; polyhydric compounds like sugars and carbon hydrates and their derivatives; and polymers. Preferred examples of such polymers include polyolefins, polybutadienes, polyvinylic alcohol, phenol condensation products, including those from a reaction with an aldehyde, polymers derived from furfurylic alcohol, polymers derivatives of styrene, divinylbenzene, naphtalene, perylene, acrylonitrile, vinyl acetate; cellulose, starch and their esters and ethers, and mixtures thereof.
- Further sources of carbon that can be used in accordance with the invention are compounds of formula CY—CY wherein Y represents a halogen or a pseudo-halogen. The term pseudo-halogen means an organic or inorganic radical susceptible of existing in the form of an ion Y− and which can form a corresponding protonated compound HY. Examples of halogen and pseudo-halogen include F, Cl, Br, I, CN, SCN, CNO, OH, N3, RCO2, RSO3 wherein R is H or an organic radical. The formation by reduction of CY bonds is preferably performed in the presence of reducing elements such as hydrogen, zinc, magnesium, Ti3+ ions, T2+ ions, Sm2+ ions, Cr2+ ions, V2+ ions, tetrakis(dialkylamino ethylene) or phosphines. These reagents can eventually be obtained or regenerated electrochemically. Further, It can also be advantageous to use catalysts increasing the reduction kinetic. Palladium or nickel derivatives are particularly efficient, particularly in the form of complexes with phosphorous or nitrogen compounds like 2,2′-bipyridine. Similarly, these compounds can be generated chemically in an active form in the presence of reducing agents, such as those mentioned above, or electrochemically. The carbonaceous material is in such instance produced by reducing the carbon-halogen bonds according to the equation:
-
CY—CY+2e −→—C═C—+2Y− - Compounds susceptible of generating carbon by reduction include perhalocarbons, particularly in the form of polymers, hexachlorobutadiene and hexachlorocyclopentadiene.
- Another way to obtain a carbonaceous material comprises the elimination of the hydrogenated compound HY, Y being as defined above, according to the equation:
-
—CH—CY—+B−→—C═C—+BHY− - Compounds susceptible of generating carbon from reduction include organic compounds comprising an even number of hydrogen atoms and Y groups, such as hydrohalocarbons, in particular in the form of polymers, such as vinylidene polyfluoride, polychloride or polybromide, or carbon hydrates. The dehydro (pseudo) halogenation can be obtained at low temperature, including room temperature, by reacting a base with the HY compound to form a salt. Example of suitable bases include tertiary basis, amines, amidines, guanidines, imidazoles, inorganic bases such as alkaline hydroxides, organometallic compounds behaving like strong bases, such as A(N(Si(CH3)3)2, LiN[CH(CH3)2]2, and butyl-lithium.
- In a preferred embodiment, the following compounds are used as sources to prepare a carbon-coated lithium-rich lithium iron phosphate Li1+xFePO4 with 0<x≦0.2: Li3PO4 as the source for Li and P, Fe3(PO4)2.8H2O as the source for Fe and P, and cellulose for carbon, wherein the Li: Fe molar ratio was 1.06:1 and the weight ratio of carbon source was 5.85 wt % (defined as mCellulose/mLi3PO4+mFe3(PO4)2.8H2O).
- For convenience, the sources of the elements utilized in accordance with the present invention are hereinafter called precursors.
- In accordance to the invention and with reference to
FIG. 2 showing the temperature (201) profile in time (202), the mixture of precursors, i.e. the mixture containing the sources of the elements utilized in the present invention, is heated up with a heating rate (203) to a temperature (204) where the sintering of the mixture takes place. Said temperature which is herein referred to as the sintering temperature is preferably at least 500° C., more preferably at least 550° C., most preferably at least 600° C. Preferably, the sintering temperature is at most 800° C., more preferably at most 750° C., most preferably at most 700° C. Preferably, the sintering temperature is between 500° C. and 800° C., more preferably between 550° C. and 750° C., most preferably between 600° C. and 700° C. The sintering temperature can be constant during the sintering process or it can vary. In case the sintering temperature varies during the sintering process, by sintering temperature in herein understood the average of the variations. The sintering temperature is considered as the temperature of the sintering chamber as measured with typical means utilized to read such high temperatures. - Preferably, said mixture is heat up with a heating rate (203) of at least 3° C./min, more preferably of at least 5° C./min, most preferably of at least 6° C./min. Preferably, said mixture is heat up with a heating rate of at most 15° C./min, more preferably of at most 10° C./min, most preferably of at most 8° C./min. Preferably, said heating rate is between 3° C./min and 15° C./min, more preferably between 5° C./min and 10° C./min, most preferably between 6° C./min and 8° C./min.
- The time used for sintering (206), hereinafter referred to as the sintering time, is preferably at least 60 min, more preferably at least 80 min, most preferably at least 100 min. Said sintering time is preferably at most 600 min, more preferably at most 300 min, most preferably at most 180 min. Said sintering time is preferably between 60 and 600 min, more preferably between 80 and 300 min, most preferably between 100 and 180 min.
- In accordance with the invention, steam is continuously injected in the sintering chamber before, during and/or after said heating up and/or said sintering of said mixture, for an injection time. By continuous injection is herein understood that fresh steam is continuously supplied to the sintering chamber throughout the injection time. For example, in one embodiment, a first steam-injection is carried out during the heating-up step for a first injection time and a second steam-injection is carried out during the sintering step for a second injection time. In another embodiment, a steam-injection is commenced during the heating-up step (207) and extended uninterruptedly to the sintering step wherein said steam-injection during sintering is carried out for at least part (208) of said sintering step. In
FIG. 2 , the time for which steam is injected is shown by the shaded area (209). It is also possible to commence the steam-injection before or during the heating up, sintering and/or cooling step. - For convenience, when a temperature is mentioned, the unit considered to express the temperature is always ° C., unless otherwise expressly indicated.
- In a first preferred embodiment of the inventive method, the steam is continuously injected in the sintering chamber during heating up said mixture of precursors to the sintering temperature. Preferably the steam injection commences (204) during said heating up when the temperature in the sintering chamber is at least a fifth of the sintering temperature, more preferably at least a third of the sintering temperature. In case a sintering temperature of between 500° C. and 800° C. is used, the steam injection preferably commences during said heating up when the temperature in the sintering chamber is at least 150° C., more preferably at least 200° C., most preferably at least 250° C.
- In a second preferred embodiment, the steam injection commences when the temperature in the sintering chamber is substantially equal with the sintering temperature (202).
- In a third preferred embodiment, the steam injection commences (207) when the temperature in the sintering chamber is below the sintering temperature but preferably at least a fifth of said sintering temperature and the steam injection is extended uninterruptedly to the sintering step; wherein said steam-injection during sintering is carried out for least part of said sintering step; wherein the steam injection during the sintering step is carried out for an injection time of at most ¼ of the total sintering time, more preferably of at most ½ of the total sintering time, most preferably of at most ¼ of the total sintering time. Preferably, the steam injection during the sintering step is carried out for an injection time of at least 1/10, more preferably of at least ⅕ of the total sintering time.
- Preferably the steam injection is uninterruptedly carried out during a total injection time of at least about ¼ of the time needed to both heat up and sinter said mixture of precursors, more preferably of at least about ⅓, most preferably of at least about ½. Preferably, said steam injection is carried out uninterruptedly during at least part of the heating up step and at least part of the sintering step. Preferably, the steam injection is extended to the sintering step, i.e. there is no discontinuity in steam injection between the heating up step and sintering step.
- In accordance with the invention, the steam is injected into the sintering chamber during an injection time, which can vary from seconds to hours. For example, in a preferred embodiment, the injection time during the heating up step is at least 25% of the total time needed to heat up said mixture of precursors to the sintering temperature, more preferably at least 50%, most preferably at least 75%. In a further preferred embodiment, the injection time during the sintering step is at least 10% of the total sintering time, more preferably at least 15%, even more preferably at least 20%, most preferably at least 75%. In a third preferred embodiment, the injection time during the heating up step is at least 25% of the total time needed to heat up said mixture of precursors to the sintering temperature, more preferably at least 50%, most preferably at least 75% and the injection time during the sintering step is at least 10% of the total sintering time, more preferably at least 15%, even more preferably at least 20%, most preferably at least 75% and there is no discontinuity in the steam injection between the heating up step and sintering step.
- In a preferred embodiment of the inventive method, steam is injected in the sintering chamber during a part, preferably the initial part, of the sintering step, the remaining part, preferably the last part, of the sintering step being carried out in a steam-free atmosphere.
- The steam is preferably injected at atmospheric pressure in the sintering chamber and is preferably water-based, i.e. water is mainly used as the liquid medium used to produce the steam. Preferably, when injected, the steam is at a temperature of at least 150° C., more preferably at least 200° C., most preferably at least 250° C. The temperature of the steam can be increased for example by mixing the water-based steam with flammable gases and igniting said gases thereby transferring heat to the steam. It is particularly advantageous to use a water-based steam and allow water to react with the precursors since better results are obtained. In particular it is preferred to adjust the steam injection such that an amount of at least 1.5 L of water per 150 g of active material participate are reacted, more preferably at least 2.0 L. most preferably at least 2.5 L. Preferably said amount of reacted water is at most 1.5 L, more preferably at most 2.0 L, most preferably at most 2.5 L. The amount of reacted water can be calculated from the difference between the amount of water introduced as steam and the amount of water captured at the end of the method of the invention.
- The steam can be supplied to and injected in the sintering chamber from a steam source via suitable piping for example. Any conventional steam sources using conventional materials and conventional steam producing methods can be used in accordance with the invention. The steam can also be collected from the sintering chamber and condensed to recover the liquid medium used to produce said steam, e.g. water.
- Preferably, the steam is injected with a flow rate of at least 10 L/min, more preferably at least 20 L/min, most preferably at least 25 L/min. Preferably, the steam is injected with a flow rate of at most 50 L/min, more preferably at most 40 L/min, most preferably at most 30 L/min.
- By sintering chamber is herein understood the chamber wherein the heating up and sintering of the mixture of precursors takes place. By injecting steam in the sintering chamber is herein understood that an atmosphere containing steam is provided in said sintering chamber.
- In accordance with the invention, the sintering chamber is provided with a stream of an inert gas. Examples of such gases include nitrogen, carbon dioxide, or noble gases such as helium or argon, or mixtures thereof. Although called inert gas, said gas may also contain small amounts of reactive gases, e.g. hydrogen. In a preferred embodiment, the inert gas is a mixture containing a small amount of a reactive gas, preferably hydrogen, and an inert gas with a majority of said inert gas; preferably in a volume ratio inert gas/H2 of 99 to 95:1 to 5 v/v, wherein the another inert gas is preferably nitrogen. The inert gas is used to blanket the reactive precursors used in accordance with the invention to prevent unwanted reactions from taking place. Preferably, the stream of inert gas is provided to the sintering chamber throughout the entire process of preparing the powders of the invention.
- After forming the inventive particles, the obtained powder is cooled to preferably room temperature. The cooling rate (210) is preferably at least 1° C./min, more preferably of at least 2° C./min, most preferably of at least 4° C./min. Preferably, said cooling rate of at most 10° C./min, more preferably of at most 7° C./min, most preferably of at most 5° C./min. Preferably, said cooling rate is between 1° C./min and 10° C./min, more preferably between 2° C./min and 7° C./min, most preferably between 4° C./min and 5° C./min.
- It is to be recognized that different implementations of the inventive method are possible, especially regarding the processing conditions, the nature of the different precursors and their sequence of blending.
- It was observed that with the inventive method, relatively short sintering times can be utilized to produce qualitative electrochemically active powders. It was also surprisingly observed that said method delivers qualitative powders in an energy saving manner and at an economical cost.
- The invention will be further explained with the help of the following examples and comparative experiments, without being however limited thereto.
-
-
- Electrochemical performances are tested in CR2032 coin type cells, with a Li foil as counter electrode in a lithium hexafluorite (LiPF6) type electrolyte at 25° C. The active material loading is 4.75 (±0.2) mg/cm2. Cells are charged to 4.0V and discharged to 2.5V to measure rate performance and capacity. The current density applied is calculated by that 1 C discharge gets 140 mAh/g specific capacity of the active materials.
- Electronic conductivity of a carbonaceous material can be measured in accordance with the method disclosed in US2002/0195591.
- Carbon structure of the samples was measured by Raman Spectroscope using a JASCO NRS 3100 High Resolution Dispersive Raman Microscope equipped with a solid state laser at a wavelength of 532 nm.
- The microstructure characterization of the samples is performed by Transmission Electron Microscopy (TEM) using a JEOL3100F Field Emission TEM.
- The particle size distribution can be determined following the methodology disclosed in WO 2005/051840.
- The BET of particles can be determined by N2 adsorption method developed by Brunauer, S., Emmett, P. H., and Teller, E., J. Am. Chem. Soc. 60: 309-319 (1938).
- Crystal sizes were determined as follows: XRD patterns were recorded on a Rigaku D/MAX 2200 PC X-ray diffractometer in the 17-144 2-theta range in a 0.02 degree scan step. Scan speed was set to 1.0 degree per minute. A goniometer with theta/2theta Bragg Brentano geometry was used having has a radius of 185 mm. A copper target X-ray tube was operated at 40 KV and 40 mA. A diffracted beam monochromator, based on a curved graphite crystal, was used to remove KBeta Cu radiation. An incident beam optic setup was used comprising a 10 mm divergent height limiting slit (DHLS), a 1-degree divergence slit (DS) and 5 degree vertical Soller slit. The diffracted beam optic setup included a 1-degree anti-scatter slit (SS), 5 degree vertical Soller slit and 0.3 mm reception slit (RS). Crystal size was calculated by Bruker AXS Topas 3.0 software, by using Rietveld refinement method as disclosed in H. M. Rietveld (1969), J. Appl. Crystallography 2 (2): 65-71
- A blend containing Fe3(PO4)2.8H2O as the source for Fe, Li3PO4 as the source for Li and PO4 and cellulose as the source for carbon, was dried in N2 at 240° C. for 1 h. The Li:Fe ratio in the blend was 1.06:1. The ratio MCellulose/(MLi3PO4+MFe3(PO4)2.8H2O) was 5.85 wt %.
- After drying, the blend was transferred into a furnace provided with an inlet for steam injection and provided with a stream of an inert gas composed of N2/H2(99:1, v/v). The blend was heated up to a sintering temperature of 600′C and sintered at that temperature for 2 h. The heating up rate was 5° C./min. Steam injection into the furnace commenced during the heating up of said furnace when the temperature in the furnace reached 250° C. and it was extended uninterrupted to the sintering step. The total steam injection time was 100 minutes. The total sintering time in the presence of steam amounted to 0.5 h. The temperature profile and an indication of when steam injection is carried out are shown in
FIG. 2 . - After sintering the obtained powder was cooled to room temperature with a cooling rate of 5° C./min.
- The process of Example 1 was repeated without using steam injection.
- Commercial carbon-coated LiFePO4 samples from Prayon (Prayon FE100, CAS No: 15365-14-7, Product code: PR-038) were investigated.
-
FIG. 3 shows Transmission Electron Microscopy (TEM) pictographs of the powders of Ex. 1 (300) and C. Exp. 1 (400) and 2 (500), respectively. The powder of Ex 1 contains particles (301) coated with a carbon coating layer (302) having a thickness of around 10 nm, whereas the carbon coatings (402 and 502) on the particles (401 and 501) forming the powders of the Comparative Experiments have a thickness of maximum about 3 nm. - Table 1 further shows the peak-intensity ratio I1360/I1580 as obtained by Raman Spectroscopy of the obtained powders. As detailed above, the ratio I1360/I1580 is an indication of the extent of carbon's graphitization. The lower the ratio I1360/I1580, the higher the extent of graphitization, i.e. the amount of highly ordered graphite in the carbon layer. Example 1 shows the lowest ratio I1360/I1580 indicating that the carbon layer has a high amount of highly ordered graphite.
-
TABLE 1 sample I1360/I1580 Ratio Example1 27447/13378 2.05 C. Exp. 1 9448/2019 4.68 C. Exp. 2 83229/27088 3.07 - The electrochemical behavior of the powders obtained by the processes of the Example and Comparative Experiments was studied in so called coin cells. A slurry was prepared by mixing the obtained powders with 10 wt % carbon black and 10 wt % PVDF into N-Methyl Pyrrolidone (NMP) and deposited on an Al foil as current collector. The obtained electrode containing 80 wt % active material was used as the positive electrode in the manufacturing of the coin cells, using a loading of 6 mg/cm2 active material. The negative electrodes were made of metallic Li. The coin cells were cycled in LiBF4 based electrolyte between 2.5 and 4 0 V at various C-rates.
- Table 2 shows the electrochemical performance of the coin cells wherein the powders of the Example, Comparative Experiments 1 and 2, respectively, were used as the active material. It is immediately observable that Example 1 shows the highest charge capacity (CQ1), highest discharge capacity (DQ1) and best rate capabilities in all C-rate tests even at a high rate as 20 C
-
TABLE 2 CQ1 DQ1 IRRQ1 Sample (mAh/g) (mAh/g) (%) 1 C 5 C 10 C 15 C 20 C DV1 DV6 Example1 159.5 157.2 1.4% 91.3% 80.3% 75.0% 72.6% 68.3% 3.383 3.057 C. Exp. 1 148.2 144.6 2.4% 90.6% 78.8% 72.2% 67.9% 64.3% 3.370 3.025 C. Exp. 2 154.0 152.9 0.7% 91.2% 76.4% 68.3% 63.2% 60.6% 3.371 3.008 - Table 3 shows the crystal sizes, obtained by the Rietveld method, of the powders.
-
TABLE 3 Crystal sample Size (nm) Example 1 70.5 Comparative Example 1 78.6 Comparative Example 2 71.8
Obviously other lithium containing electrochemically active powders may be prepared by analogous methods by using different starting material. In particular, phosphates of other transition metals such as Mn, Co, Ni. V, Cr, Ti, Mo, Nb, and W may be used instead of or in addition to Fe3(PO4)2.8H2O to prepare Lithium metal phospates according to the invention with mixed metal or with metals other than Fe.
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CN115050945A (en) * | 2022-07-15 | 2022-09-13 | 湖北工业大学 | Preparation method of biomass nitrogen-doped carbon-coated lithium-rich lithium iron phosphate positive electrode material |
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Cited By (8)
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US20160285092A1 (en) * | 2015-03-24 | 2016-09-29 | Nichia Corporation | Positive electrode active material for nonaqueous electrolyte secondary battery |
US9966601B2 (en) * | 2015-03-24 | 2018-05-08 | Nichia Corporation | Positive electrode active material for nonaqueous electrolyte secondary battery |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
US10938030B2 (en) | 2017-04-28 | 2021-03-02 | Samsung Electronics Co., Ltd. | Positive active material, positive electrode and lithium secondary battery containing the material, and method of preparing the material |
US11094936B2 (en) * | 2019-10-16 | 2021-08-17 | Hcm Co., Ltd. | Tungsten-doped lithium manganese iron phosphate-based particulate, tungsten-doped lithium manganese iron phosphate-based powdery material including the same, and method for preparing powdery material |
US11967717B2 (en) | 2019-10-16 | 2024-04-23 | Hcm Co., Ltd. | Tungsten-doped lithium manganese iron phosphate-based particulate and tungsten-doped lithium manganese iron phosphate-based powdery material including the same |
CN115050945A (en) * | 2022-07-15 | 2022-09-13 | 湖北工业大学 | Preparation method of biomass nitrogen-doped carbon-coated lithium-rich lithium iron phosphate positive electrode material |
CN116040674A (en) * | 2023-02-08 | 2023-05-02 | 成都理工大学 | Surface coating technology of inorganic powder material with high efficiency and low cost |
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EP3053208B1 (en) | 2019-01-02 |
WO2015049105A1 (en) | 2015-04-09 |
HUE042280T2 (en) | 2019-06-28 |
EP3053208A1 (en) | 2016-08-10 |
PL3053208T3 (en) | 2019-06-28 |
TW201519496A (en) | 2015-05-16 |
JP2016534494A (en) | 2016-11-04 |
KR101900579B1 (en) | 2018-09-19 |
JP6324498B2 (en) | 2018-05-16 |
TWI544676B (en) | 2016-08-01 |
US20230335746A1 (en) | 2023-10-19 |
KR20160066549A (en) | 2016-06-10 |
CN105612640B (en) | 2017-12-12 |
CN105612640A (en) | 2016-05-25 |
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