JP5665742B2 - 充電式リチウム電池用のカソード活性材料としてのリチウム金属ホスフェート/炭素ナノコンポジット - Google Patents
充電式リチウム電池用のカソード活性材料としてのリチウム金属ホスフェート/炭素ナノコンポジット Download PDFInfo
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- JP5665742B2 JP5665742B2 JP2011521664A JP2011521664A JP5665742B2 JP 5665742 B2 JP5665742 B2 JP 5665742B2 JP 2011521664 A JP2011521664 A JP 2011521664A JP 2011521664 A JP2011521664 A JP 2011521664A JP 5665742 B2 JP5665742 B2 JP 5665742B2
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- Prior art keywords
- carbon
- phosphate
- precursor
- lithium
- lithium metal
- 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.)
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 54
- 229910019142 PO4 Inorganic materials 0.000 title claims description 42
- 239000010452 phosphate Substances 0.000 title claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 38
- 229910052799 carbon Inorganic materials 0.000 title claims description 37
- 229910052744 lithium Inorganic materials 0.000 title claims description 34
- 239000002114 nanocomposite Substances 0.000 title claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 11
- 239000006182 cathode active material Substances 0.000 title claims description 4
- 239000002243 precursor Substances 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 235000011007 phosphoric acid Nutrition 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 150000001721 carbon Chemical class 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- -1 phosphate ester Chemical class 0.000 claims description 4
- IHTFTOGFXXXQBO-UHFFFAOYSA-B [C+4].[C+4].[C+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [C+4].[C+4].[C+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O IHTFTOGFXXXQBO-UHFFFAOYSA-B 0.000 claims description 3
- 238000005087 graphitization Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea 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
- 241000219146 Gossypium Species 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000007799 cork Substances 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- VUNHSSYEAVRURP-UHFFFAOYSA-N [C].[O].[P] Chemical compound [C].[O].[P] VUNHSSYEAVRURP-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 235000019241 carbon black Nutrition 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 235000014571 nuts Nutrition 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000760 Hardened steel Inorganic materials 0.000 description 2
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 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
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- NPLZZSLZTJVZSX-UHFFFAOYSA-L iron(2+);oxalate;dihydrate Chemical compound O.O.[Fe+2].[O-]C(=O)C([O-])=O NPLZZSLZTJVZSX-UHFFFAOYSA-L 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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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- 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
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- 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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- 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
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Description
a)リン酸またはリン酸塩またはリン酸エステルを含む活性化剤をセルロース質前駆体に含浸するステップ、
b)含浸セルロース質前駆体を約450℃から約800℃の温度まで加熱することによって大比表面積のリン酸化炭素を生成するステップ、
c)こうして得られたリン酸化炭素をリチウム、遷移金属、任意選択のドーパントおよび必要であれば追加のホスフェートの前駆体と混合するステップ、
d)ステップc)の混合物を約450℃から約800℃の温度まで加熱することによってリチウム金属ホスフェートと炭素とのナノコンポジットを生成するステップを含む。
セルロース粉末(2g)を85%H3PO4(2g)と水(4g)の溶液で含浸し、空気中で周囲温度から470℃まで1時間以内で加熱した。硫酸/硝酸で試料を温浸した後、得られた活性化炭素のリン含量をリンモリブデンブルー法によって測定した結果は9.1mmolP/gであった。
Claims (9)
- 充電式電池のカソード活性材料としてのリチウム金属ホスフェート/炭素ナノコンポジットを合成するための方法であって、リン酸化炭素と、リチウムおよび遷移金属の前駆体を混合し反応させることを含む方法。
- 以下のステップ:
a)リン酸またはリン酸塩またはリン酸エステルを含む活性化剤をセルロース質前駆体に含浸するステップ、
b)含浸セルロース質前駆体を加熱することによって大比表面積のリン酸化炭素を生成するステップ、
c)前記リン酸化炭素をリチウムおよび遷移金属の前駆体と混合するステップ、
d)ステップc)の混合物を加熱することによってリチウム金属ホスフェートと炭素のナノコンポジットを生成するステップ
を含む、請求項1に記載の方法。 - セルロース質前駆体が、木材、農業残渣、ナッツ殻、ナッツ種、果実核、木綿、麻、ジュート、樹皮、コルク、セルロースパルプ、紙またはそれらの混合物である、請求項2に記載の方法。
- セルロース質前駆体が、セルロースパルプ、紙もしくは木綿またはそれらの混合物である、請求項2に記載の方法。
- セルロース質前駆体が、0.1から5.0の範囲の含浸比(ホスフェートまたはリン酸とセルロース質前駆体の乾燥基準の重量比)で、オルトリン酸H3PO4を用いて含浸される、請求項2に記載の方法。
- グラファイト化触媒がステップa)で添加される、請求項2に記載の方法。
- ステップa)の含浸セルロース質前駆体が、450℃から1000℃の範囲の温度まで加熱される、請求項2に記載の方法。
- 含浸セルロース質前駆体が発泡される、請求項7に記載の方法。
- 炭素が、炭素−酸素−リン(C−O−P)ブリッジを介してリチウム金属ホスフェートと共有結合している、請求項1に従って得られるリチウム金属ホスフェート/炭素ナノコンポジット。
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PCT/IB2009/053300 WO2010015969A2 (en) | 2008-08-05 | 2009-07-29 | Lithium metal phosphate/carbon nanocomposites as cathode active materials for rechargeable lithium batteries |
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