JP6257650B2 - リチウム二次電池用正極複合素材製造方法及びこれを用いた電極製造方法 - Google Patents
リチウム二次電池用正極複合素材製造方法及びこれを用いた電極製造方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims description 68
- 229910052744 lithium Inorganic materials 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 35
- 239000000243 solution Substances 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 239000011572 manganese Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 19
- 239000008139 complexing agent Substances 0.000 claims description 18
- 239000007858 starting material Substances 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 17
- 238000000975 co-precipitation Methods 0.000 claims description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 2
- 229910002982 Li2MnO3 phase Inorganic materials 0.000 claims 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 150000004696 coordination complex Chemical class 0.000 claims 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 12
- 238000007599 discharging Methods 0.000 description 9
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 229910014689 LiMnO Inorganic materials 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910015118 LiMO Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000252233 Cyprinus carpio Species 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M10/0422—Cells or battery with cylindrical casing
- H01M10/0427—Button cells
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- H01M10/052—Li-accumulators
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- H01M4/00—Electrodes
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- 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
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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Description
特に、電気自動車は1回充電走行距離が極めて重要であり、これは二次電池正極素材のエネルギー密度に関するため、正極素材の高性能化に対する研究開発が必須である。従来のLMO又はNMC、そして、オリビン系正極素材のエネルギー密度は、約120〜150mAh/gのレベルに電気自動車の走行距離を画期的に向上させるためには不足であると言える。
一実施形態によると、前記正極複合素材Li(LixNiyCozMnwO2+α)のXRD(X−Ray Diffraction、X線回折)の分析結果、2つの超格子ピークを示す。ここで、前記2つの超格子ピークが検出される前記2次焼成温度は800℃以上である。
Claims (14)
- 硝酸ニッケル溶液、硝酸マンガン溶液、及び硝酸コバルト溶液を混合した出発物質溶液に錯化剤を混合して金属錯体を形成し、前記出発物質溶液と前記錯化剤との混合溶液のpHを調整するためにNaOH水溶液を添加し、共沈法を用いて、Li2MnO3相及びNMC相を含み前記Li2MnO3相の比率が重量比で21.3%〜29.2%である正極複合素材の前駆体を製造するステップと、
前記前駆体にLiOH・H2Oを投入して混合するステップと、
前記混合した粉末を1次焼成するステップと、
前記1次焼成した粉末を2次焼成するステップと、
を含み、前記出発物質溶液は、Ni(NO3)2・H2O、Mn(NO3)2・H2O及びCo(NO3)2・H2Oをそれぞれ1:4:1のモル比で混合した溶液であり、前記錯化剤としてアンモニア水を使用し、前記出発物質溶液に前記錯化剤を0.8モル混合する、リチウム二次電池用正極複合素材製造方法。 - 前記1次焼成するステップでの焼成温度が500℃である、請求項1に記載のリチウム二次電池用正極複合素材製造方法。
- 前記2次焼成するステップでの焼成温度が650℃〜1000℃である、請求項1又は請求項2に記載のリチウム二次電池用正極複合素材製造方法。
- 前記正極複合素材のXRD(X−Ray Diffraction、X線回折)の分析結果が、2つの超格子ピークを示す、請求項1〜請求項3のいずれか一項に記載のリチウム二次電池用正極複合素材製造方法。
- 前記2つの超格子ピークは、前記2次焼成するステップでの焼成温度を800℃以上の温度としたときに形成される、請求項4に記載のリチウム二次電池用正極複合素材製造方法。
- 前記NaOH水溶液は、NaOH粉末を溶液に溶解した1モルの溶液である、請求項1〜請求項5のいずれか一項に記載のリチウム二次電池用正極複合素材製造方法。
- 前記LiOH・H2Oは前記前駆体対比103wt%の量で添加される、請求項1〜請求項6のいずれか一項に記載のリチウム二次電池用正極複合素材製造方法。
- 共沈法を用いて、Li2MnO3相及びNMC相を含み前記Li2MnO3相の比率が重量比で21.3%〜29.2%である正極複合素材粉末を製造するステップと、
前記正極複合素材粉末に導電剤とバインダーとを混合してスラリーを製造するステップと、
前記スラリーを塗布するステップと、
前記塗布されたスラリーを乾燥するステップと、
前記乾燥されたスラリーを押し付けるステップと、
前記押し付けられたスラリーをパンチングして正極を製造するステップと、
前記正極を用いて電極セルを製造するステップと、
を含み、
ここで、Li2MnO3相及びNMC相を含み前記Li2MnO3相の比率が重量比で21.3%〜29.2%である正極複合素材粉末の前記製造ステップは、
硝酸ニッケル溶液、硝酸マンガン溶液、及び硝酸コバルト溶液を混合した出発物質溶液に錯化剤を混合して金属錯体を形成し、前記出発物質溶液と前記錯化剤との混合溶液のpHを調整するためにNaOH水溶液を添加し、共沈法を用いてLi2MnO3相及びNMC相を含み、前記Li2MnO3相の比率は重量比で21.3%〜29.2%である正極複合素材の前駆体を製造するステップと、
前記前駆体にLiOH・H2Oを投入して混合するステップと、
前記混合した粉末を1次焼成するステップと、
前記1次焼成した粉末を2次焼成するステップと、
を含み、前記出発物質溶液は、Ni(NO3)2・H2O、Mn(NO3)2・H2O及びCo(NO3)2・H2Oをそれぞれ1:4:1のモル比で混合した溶液であり、前記錯化剤としてアンモニア水を使用し、前記出発物質溶液に前記錯化剤を0.8モル混合する、リチウム二次電池の電極製造方法。 - 前記電極セルを製造するステップでは、コインセル形態又は3極セルの形態の電池セルが形成される、請求項8に記載のリチウム二次電池の電極製造方法。
- 前記コインセルにおいては、前記製造された正極を使用し、負極にリチウムメタルを使用し、隔離膜にPE Separatorを使用し、電解液にエチレンカーボネイト(EC)とジエチルカーボネイト(DMC)の混合溶媒(体積比1:1)に1モルLiPF6が溶解した溶液を使用する、請求項9に記載のリチウム二次電池の電極製造方法。
- 前記3極セルにおいては、前記製造された正極を使用し、対極にリチウムメタルを使用し、参照電極にリチウムメタルを使用し、隔離膜にPE Separatorを使用し、電解液にエチレンカーボネイト(EC)とジエチルカーボネイト(DMC)の混合溶媒(体積比1:1)に1モルLiPF6が溶解した溶液を使用する、請求項9又は請求項10に記載のリチウム二次電池の電極製造方法。
- 前記スラリーは、前記複合素材粉末、導電剤、及びバインダーの組成比を80:10:10の重量比(wt%)で混合したものである、請求項8〜請求項11のいずれか一項に記載のリチウム二次電池の電極製造方法。
- 前記スラリーを塗布するステップでは、前記スラリーをアルミホイルに100〜110μmの厚さに塗布する、請求項8〜請求項12のいずれか一項に記載のリチウム二次電池の電極製造方法。
- 前記乾燥されたスラリーを押し付けるステップでは、乾燥されたスラリーを前記アルミホイルに押し付けて60〜70μmの厚さにする、請求項13に記載のリチウム二次電池の電極製造方法。
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