CN102137811A - 作为阴极活性材料用于可再充锂电池的锂金属磷酸盐/碳纳米复合材料 - Google Patents
作为阴极活性材料用于可再充锂电池的锂金属磷酸盐/碳纳米复合材料 Download PDFInfo
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- CN102137811A CN102137811A CN2009801293863A CN200980129386A CN102137811A CN 102137811 A CN102137811 A CN 102137811A CN 2009801293863 A CN2009801293863 A CN 2009801293863A CN 200980129386 A CN200980129386 A CN 200980129386A CN 102137811 A CN102137811 A CN 102137811A
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- Prior art keywords
- precursor
- carbon
- lithium
- phosphoric acid
- described method
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 5
- 239000010452 phosphate Substances 0.000 title abstract description 5
- 239000006182 cathode active material Substances 0.000 title abstract 2
- 239000002243 precursor Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 235000021317 phosphate Nutrition 0.000 claims description 34
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 27
- 239000001913 cellulose Substances 0.000 claims description 22
- 229920002678 cellulose Polymers 0.000 claims description 22
- 150000003016 phosphoric acids Chemical class 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 15
- 235000011007 phosphoric acid Nutrition 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 230000026731 phosphorylation Effects 0.000 claims description 11
- 238000006366 phosphorylation reaction Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000005418 vegetable material Substances 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 claims description 4
- 235000014571 nuts Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 241001133760 Acoelorraphe Species 0.000 claims description 2
- 244000144725 Amygdalus communis Species 0.000 claims description 2
- 235000011437 Amygdalus communis Nutrition 0.000 claims description 2
- 244000144730 Amygdalus persica Species 0.000 claims description 2
- 241000167854 Bourreria succulenta Species 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 240000000491 Corchorus aestuans Species 0.000 claims description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 241000219146 Gossypium Species 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 240000007817 Olea europaea Species 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 235000020224 almond Nutrition 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 235000019693 cherries Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000007799 cork Substances 0.000 claims description 2
- 238000005187 foaming Methods 0.000 claims description 2
- 238000005087 graphitization Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011122 softwood Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 230000006866 deterioration Effects 0.000 claims 3
- 229910000765 intermetallic Inorganic materials 0.000 claims 2
- 229910000616 Ferromanganese Inorganic materials 0.000 claims 1
- 238000002441 X-ray diffraction Methods 0.000 claims 1
- OTBRCBRNTVKMRU-UHFFFAOYSA-N [C].OP(O)(O)=O Chemical compound [C].OP(O)(O)=O OTBRCBRNTVKMRU-UHFFFAOYSA-N 0.000 claims 1
- VUNHSSYEAVRURP-UHFFFAOYSA-N [C].[O].[P] Chemical compound [C].[O].[P] VUNHSSYEAVRURP-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims 1
- 229920005610 lignin Polymers 0.000 claims 1
- 150000002642 lithium compounds Chemical class 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims 1
- 230000003595 spectral effect Effects 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000001721 carbon Chemical class 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 2
- 244000274906 Quercus alba Species 0.000 description 2
- 235000009137 Quercus alba Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 carbon (phosphorylated carbon Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 241000218314 Liriodendron tulipifera Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HSNVNALJRSJDHT-UHFFFAOYSA-N P(=O)(=O)[Mo] Chemical compound P(=O)(=O)[Mo] HSNVNALJRSJDHT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical compound [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
- C04B35/62209—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse using woody material, remaining in the ceramic 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
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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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
- H01M4/5805—Phosphides
-
- H—ELECTRICITY
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
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Abstract
本发明提供一种用于合成在可再充电化学电池中作为阴极活性材料的锂金属磷酸盐/碳纳米复合材料的方法，所述方法包括：将锂的前体，一种或多种过渡金属的前体和磷酸盐或酯的前体与高表面积活性炭优选磷酸化碳混合并反应。
Description
发明领域
本发明涉及在可再充电化学电池中作为阴极活性材料的锂金属磷酸盐/碳纳米复合材料。
背景技术
在可再充锂离子电池中作为阴极活性材料的锂过渡金属磷酸盐/碳纳米复合材料，特别是LiFePO4/C和LixMnyFe1-yPO4/C，已经显示即使在高的充电/放电比率的情况下，也获得优异的充电能力。如之前由我们1所公开的，这样的锂金属磷酸盐/碳纳米复合材料可以通过下列方法获得：将锂的合适前体，过渡金属的合适前体和磷酸盐与高表面积的炭黑或石墨一起研磨，之后在较低温度(400℃至600℃)结晶。研磨导致石墨烯(graphene)平面破坏并且在石墨烯边缘产生高反应性配位不饱和碳原子(悬空键)，其可以与磷酸盐基团形成共价键，或经由氧与过渡金属中心形成共价键。由此获得的纳米尺寸的锂金属磷酸盐前体的混合物已经在较低温度结晶，其与共价结合的碳组合防止晶体生长并且产生锂金属磷酸盐纳米粒子和碳的纳米复合材料。锂金属磷酸盐的小的粒子尺寸和与导电碳的紧密接触使得即使使用接近绝缘的材料比如LixMnyFe1-yPO4也可以有良好的电化学性能。
使用高表面积炭黑可以获得初级尺寸足够小(约50nm)的锂金属磷酸盐/碳纳米复合材料，所述高表面积炭黑在研磨过程中容易破坏并且提供大量的用于与锂金属磷酸盐的前体反应的活性部位。然而，这样的高表面积炭黑对于制备而言昂贵并且能量集约，通常通过在远高于1000℃的温度热解石油衍生物而产生2。
锂金属磷酸盐/碳纳米复合材料还可以使用石墨合成，石墨在研磨过程中首先通过剪切力层离成石墨烯多层片，然后进一步破坏为在边缘具有活性部位的更小的纳米石墨烯片。尽管合成石墨比高表面积炭黑更廉价，但是它们通过碳在高温(高于2500℃)的石墨化的生产甚至更是能量集约的2。而且，石墨与高表面积炭黑相比需要更长或更多的能量研磨，以将它们减小至纳米尺度尺寸。通过使用高表面积石墨可以减少研磨时间，这可以例如通过酸插层石墨(acid intercalated graphite)的快速热膨胀来获得3。然而，这样的辅助生产步骤再次增加了生产成本。
发明描述
本发明关注使用活性炭的锂金属磷酸盐/碳纳米复合材料的合成。优选地，所述合成使用高表面积磷酸化碳(phosphorylated carbon)，即，具有共价结合的磷酸盐基团的碳，所述具有共价结合的磷酸盐基团的碳是通过碳质植物材料的磷酸活化而得到的，所述碳质植物材料优选是纤维素或木素纤维材料，比如木材或农业残余物。这种方法具有使用廉价，可再生的碳资源和明显更少能量的优点，原因在于与高表面积炭黑或石墨的制备所需要的工艺温度相比，碳活化所需要的工艺温度远低得多。而且，相当有利于随后与锂和过渡金属前体形成所需的锂金属磷酸盐/碳纳米复合材料的反应，因为具有共价结合磷酸盐基团的高表面积碳已经通过植物材料的空心纤维或多孔结构的磷酸活化而获得。这样降低或甚至消除了用于通过研磨的机械活化的时间和能量要求。
根据本发明的锂金属磷酸盐/碳纳米复合材料的合成包括下列步骤：
a)用包含磷酸或磷酸盐或磷酸酯的活化剂浸渍纤维素前体，
b)加热经浸渍的纤维素前体至约450℃至约800℃的温度，以产生高比表面积的磷酸化碳，
c)将由此获得的磷酸化碳与锂的前体，过渡金属的前体，任选的掺杂剂的前体，以及必要时的另外的磷酸盐或酯(phosphate))的前体混合，
d)将步骤c)的混合物在约450℃至约800℃的温度加热以制备锂金属磷酸盐和碳的纳米复合材料。
合适的纤维素前体是植物材料比如木材(例如，硬木材，软木材，木屑，木粉，锯屑)，农业残余物，比如稻草，坚果壳(例如，椰子，杏仁或棕榈坚果壳)，坚果核，水果果核(例如，橄榄，樱桃或桃的核)，棉，亚麻，黄麻，树皮，软木，纤维素浆，纸等等。优选产生低机械强度的活性炭的材料，因为这样有利于随后形成具有锂金属磷酸盐的纳米复合材料。这样的材料的典型特征在于低的重量密度和低的木质素粘合剂含量，例如纤维素浆，纸或棉。优选地，所述材料具有低的灰含量。如果需要，可以例如通过使用酸的沥滤来降低纤维素前体的灰含量。优选地，将纤维素前体干燥，并且通过压碎，碾磨，研磨等来降低粒度。
在所述方法的步骤a)中，使用磷酸或磷酸盐或磷酸酯的溶液，优选使用正磷酸H3PO4来浸渍纤维素前体。合适的浸渍比在约0.1至约5.0的范围内，所述浸渍比被限定为磷酸或磷酸盐或酯(phosphate)与纤维素前体(干基)的重量比。优选的浸渍比在约0.5至约1.5的范围内。任选地，可以添加石墨化催化剂，比如铁化合物，以提高最终产品的导电性。
在所述方法的步骤b)中，将由此经浸渍的纤维素前体首先加热以将其干燥，然后再形成(from)共价的碳-磷酸键(磷酸化)，将前体脱水，并且最终形成导电的高比表面积的磷酸化碳。
据报道4-8，在磷酸酯的形成下，磷酸已经与纤维素在低于150℃反应。磷酸盐或酯和多磷酸盐或酯物种的交联降低了挥发物在更高温度的释放，由此改善了碳收率。前体结构在约250℃至450℃的膨胀产生了高比表面积(典型高于1000m2/g)的微孔和中孔的磷酸化碳。超过450℃，磷酸酯键变得不稳定，并且磷酸盐或酯由于蒸发而缓慢损失.9，10。在高于450℃，原子簇尺寸和由此的碳的导电性快速增加。
根据本发明，经浸渍的纤维素前体被加热至在约450℃至约1000℃，优选450℃至800℃，更优选450℃至600℃的范围内的温度。加热速率应当足够低，以允许挥发物(主要是水)散逸，而不将材料吹胀；或应当足够高，以通过发泡来疏松其结构。为了通过部分石墨化来提高碳的导电性，在没有由于蒸发而导致的大量磷酸盐或酯损失的情况下，高于450℃的热处理应当及时减小到最低。
热处理可以在空气中进行，因为磷酸酯基团保护碳一定程度上不氧化11，12。然而，高于450℃的热处理优选在惰性气体气氛比如氮气或氩气中进行。为了降低由于蒸发所带来的磷酸盐或酯的损失，可以增加气体压力。由此获得的高表面积碳的孔至少部分地被多磷酸填充，其与由磷酸活性炭制备吸附剂相反，不需要用水提取，因为它在用于锂金属磷酸盐的进一步的反应中用作前体。
在所述方法的步骤c)中，将来自步骤b)的高表面积磷酸化碳与锂的前体，一种或多种过渡金属的前体，任选的掺杂剂，以及必要时的另外的磷酸盐或酯，以合适的用于合成所需的锂金属磷酸盐/碳纳米复合材料的量混合。锂金属磷酸盐/碳纳米复合材料的最终碳含量在优选约1％至约20％，并且更优选1％至10％的范围内。
优选的锂的前体是Li2CO3，Li2O，LiOH，LiH2PO4，Li2HPO4，Li3PO4，偏磷酸锂，或多磷酸锂。
优选的过渡金属前体是金属碳酸盐，或草酸盐，或氧化物，氢氧化物，与羧酸的盐(例如，乙酸盐)或羟基羧酸的盐(例如，乙醇酸盐，乳酸盐，柠檬酸盐，酒石酸盐)，氯化物，硫酸盐或硝酸盐。
优选的磷酸盐或酯的前体是H3PO4，HPO3，P2O5，LiH2PO4，Li2HPO4，Li3PO4，偏磷酸锂或多磷酸锂，NH4H2PO4，(NH4)2HPO4。
在一个优选的实施方案中，混合在干燥状态进行。用于干燥混合的优选方法是研磨，并且更优选的是球磨研磨。在干燥混合的情况下，应当选择前体，以使得反应的任何副产物都是挥发性的，例如，H2O，CO2，NH3，NO2。
在另一个优选的实施方案中，混合在液相中进行。更优选地，混合在水相中进行。前体优选逐步混合，例如，首先将磷酸化碳与过渡金属前体和另外的磷酸或磷酸盐或酯混合，之后用所需量的LiOH溶液或Li2CO3中和。不适宜的反应副产物可以通过洗涤从固体产物中移除，例如，Cl-，HCO3-，SO42-，NO3-，NH4+，等等。
混合可以在空气中进行，或必要时，在惰性气体或还原气氛中进行，以防止氧化，例如Fe2+的氧化。在混合过程中的反应速率可以通过加热而提高。
在所述方法的步骤d)中，将步骤c)的混合物加热至约400℃至约800℃的温度以进行结晶。这个温度影响锂金属磷酸盐/碳纳米复合材料的结晶尺寸，因此影响其电化学性能。优选地，所述温度在约450℃至约600℃的范围内。优选地，这种热处理在惰性气体气氛比如氮气或氩气中进行，以避免被空气氧化。必要时，可以使用反应性气氛，例如含有H2，CO/CO2或H2O/CO2的还原气氛。
实施例1：LiMn0.8Fe0.2PO4/C纳米复合材料的合成
纤维素粉末(2g)用85％H3PO4(2g)和水(4g)的溶液浸渍，并且在空气中，在1小时内从环境温度加热至470℃。在使用硫酸/硝酸对样品进行浸煮之后，采用磷钼蓝方法(phosphomolybdenum blue method)确定所得活性炭的磷含量，测得为9.1mmol P/g。
将磷酸化碳(1.43g)，MnCO3(2.76g)，二水合草酸Fe(II)(1.08g)，LiH2PO4(1.77g)和Li2CO3(0.48g)在硬质钢容器中使用硬质钢球，在行星球磨机Retsch PM 100)中于500rpm进行研磨2小时。在氩气流中，在30分钟内将所得粉末加热至470℃，并且在该温度保持1小时。所得LiMn0.8Fe0.2PO4/C纳米复合材料的碳含量为8重量％。
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Claims (28)
1.一种用于合成在可再充电化学电池中作为阴极活性材料的锂金属磷酸盐/碳纳米复合材料的方法，所述方法包括：将锂的前体，一种或多种过渡金属的前体和磷酸盐或酯的前体与高表面积活性炭优选磷酸化碳混合并反应。
2.根据权利要求1所述的方法，所述方法包括下列步骤：
a)用包含磷酸或磷酸盐或磷酸酯的活化剂浸渍纤维素前体，
b)加热经浸渍的纤维素前体，以产生高比表面积的磷酸化碳，
c)将由此获得的磷酸化碳与锂的前体，过渡金属的前体，任选的掺杂剂的前体，以及必要时的另外的磷酸盐或酯的前体混合，
d)将步骤c)的混合物加热以制备锂金属磷酸盐和碳的纳米复合材料。
3.根据权利要求2a)所述的方法，其中所述纤维素前体是植物材料，如木材(例如，硬木材，软木材，木屑，木粉，锯屑)，农业残余物，比如稻草，坚果壳(例如，椰子，杏仁或棕榈坚果壳)，坚果核，水果果核(例如，橄榄，樱桃或桃的核)，棉，亚麻，黄麻，树皮，软木，纤维素浆，纸，或它们的混合物。
4.根据权利要求2a)所述的方法，其中所述纤维素前体具有低的重量密度。
5.根据权利要求2a)所述的方法，其中所述纤维素前体具有低的木质素含量。
6.根据权利要求2a)所述的方法，其中所述纤维素前体具有低的灰含量。
7.根据权利要求2a)所述的方法，其中所述纤维素前体是纤维素浆，纸或棉，或它们的混合物。
8.根据权利要求2a)所述的方法，其中所述纤维素前体用磷酸或磷酸盐或磷酸酯的溶液浸渍，优选用正磷酸H3PO4浸渍，其中浸渍比(磷酸盐或酯或磷酸与以干基计的纤维素前体的重量比)在约0.1至5.0，优选约0.5至约2.0的范围内。
9.根据权利要求2a)所述的方法，其中在步骤a)中添加石墨化催化剂，比如金属化合物，优选铁化合物。
10.根据权利要求2b)所述的方法，其中将步骤a)的经浸渍的纤维素前体逐渐加热至在约450℃至约1000℃，优选约450℃至约800℃并且更优选约450℃至约600℃的范围内的温度。
11.根据权利要求10所述的方法，其中加热速率足够低，从而允许挥发物散逸而不将材料吹胀。
12.根据权利要求10所述的方法，其中加热速率足够高，从而通过发泡而疏松材料的结构。
13.根据权利要求10所述的方法，其中在加热至约450℃之后，在短时间内并且优选在不存在氧的情况下，使温度升高到约500℃至约1000℃，优选约500℃至约800℃并且更优选约500℃至约600℃，以在没有由于蒸发而导致的大量磷酸盐或酯损失的情况下增加导电性。
14.根据权利要求2c)所述的方法，其中所述锂的前体是Li2CO3，Li2O，LiOH，LiH2PO4，Li2HPO4，Li3PO4，偏磷酸锂或多磷酸锂，或不产生使主要产物劣化的副产物的任何其它锂化合物，或它们的混合物。
15.根据权利要求2c)所述的方法，其中所述金属的前体是金属碳酸盐，或草酸盐，或氧化物，氢氧化物，与羧酸的盐(例如，乙酸盐)或与羟基羧酸的盐(例如，乙醇酸盐，乳酸盐，柠檬酸盐，酒石酸盐)，氯化物，硫酸盐，硝酸盐，或不产生使主要产物劣化的副产物的任何其它金属化合物，或它们的混合物。
16.根据权利要求2c)所述的方法，其中所述磷酸盐或酯的前体是H3PO4，HPO3，P2O5，LiH2PO4，Li2HPO4，Li3PO4，偏磷酸锂或多磷酸锂，NH4H2PO4，(NH4)2HPO4，或不产生使主要产物劣化的副产物的任何磷酸盐化合物，或它们的混合物。
17.根据权利要求2c)所述的方法，其中混合是在干燥状态进行的，优选通过研磨进行，并且更优选通过球磨研磨进行。
18.根据权利要求2c)所述的方法，其中混合是在液相中进行的，优选在水相中进行。
19.根据权利要求2d)所述的方法，其中优选在惰性气体或还原气氛下，将步骤c)的产物加热至约400℃至约800℃，优选约450℃至约600℃的温度以进行结晶。
20.根据权利要求1获得的锂金属磷酸盐/碳纳米复合材料，其中碳含量在约1重量％至约20重量％的范围内，优选在约1重量％至约10重量％的范围内。
21.根据权利要求1获得的锂金属磷酸盐/碳纳米复合材料，其中锂金属磷酸盐域的平均微晶尺寸(例如，由X-射线衍射谱线增宽确定)小于约200nm，优选小于约100nm，并且更优选小于约60nm。
22.根据权利要求1获得的锂金属磷酸盐/碳纳米复合材料，其中锂金属磷酸盐域的平均横截面尺寸(例如，由电子显微镜确定)小于约200nm，优选小于约100nm，并且更优选小于约60nm。
23.根据权利要求1获得的锂金属磷酸盐/碳纳米复合材料，其中所述碳经由碳-氧-磷(C-O-P)桥共价结合到所述锂金属磷酸盐。
24.根据权利要求1获得的锂金属磷酸盐/碳纳米复合材料，其中所述锂金属磷酸盐是任选掺杂有其它元素的磷酸锂铁LixFePO4。
25.根据权利要求1获得的锂金属磷酸盐/碳纳米复合材料，其中所述锂金属磷酸盐是任选掺杂有其它元素的磷酸锂锰铁LixMnyFe1-yPO4。
26.一种可再充电池，所述可再充电池包括阴极，阳极和电解质，所述阴极包含根据权利要求20至25所述的锂金属磷酸盐/碳纳米复合材料。
27.根据权利要求26所述的可再充电池，其中所述阴极还包含导电性添加剂。
28.根据权利要求26所述的可再充电池，其中所述阴极还包含粘合剂。
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| CA2732854A1 (en) | 2010-02-11 |
| US20110136014A1 (en) | 2011-06-09 |
| JP5665742B2 (ja) | 2015-02-04 |
| KR101628416B1 (ko) | 2016-06-08 |
| JP2011530153A (ja) | 2011-12-15 |
| WO2010015969A2 (en) | 2010-02-11 |
| CA2732854C (en) | 2016-10-25 |
| US8435677B2 (en) | 2013-05-07 |
| EP2331458A2 (en) | 2011-06-15 |
| WO2010015969A3 (en) | 2010-12-02 |
| KR20110053985A (ko) | 2011-05-24 |
| EP2331458B1 (en) | 2018-12-12 |
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