JP2022553263A - リチウム二次電池正極活物質、その製造方法、及びこれを含むリチウム二次電池 - Google Patents
リチウム二次電池正極活物質、その製造方法、及びこれを含むリチウム二次電池 Download PDFInfo
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- JP2022553263A JP2022553263A JP2022523167A JP2022523167A JP2022553263A JP 2022553263 A JP2022553263 A JP 2022553263A JP 2022523167 A JP2022523167 A JP 2022523167A JP 2022523167 A JP2022523167 A JP 2022523167A JP 2022553263 A JP2022553263 A JP 2022553263A
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- Prior art keywords
- active material
- lithium
- secondary battery
- positive electrode
- chemical formula
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- 239000007774 positive electrode material Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000011247 coating layer Substances 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000011164 primary particle Substances 0.000 claims description 39
- 239000006182 cathode active material Substances 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 21
- 239000002019 doping agent Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 230000004907 flux Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 8
- 239000011163 secondary particle Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 150000002642 lithium compounds Chemical class 0.000 claims description 3
- -1 Al ( OH) 3 Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 239000011149 active material Substances 0.000 claims 1
- 230000004931 aggregating effect Effects 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 238000010586 diagram Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011572 manganese Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000001351 cycling effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910004320 Li(NixCoyMnz)O2 Inorganic materials 0.000 description 2
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 2
- 229910002982 Li2MnO3 phase Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 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
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 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 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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- 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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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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Abstract
Description
[化1]rLi2MnO3・(1-r)LiaNixCoyMnzM11-(x+y+z)O2
(前記化学式1において、0<r≦0.6、0<a≦1、0≦x≦1、0≦y<1、0≦z<1、及び0<x+y+z≦1であり、前記M1は、Na、K、Mg、Al、Fe、Cr、Y、Sn、Ti、B、P、Zr、Ru、Nb、W、Ba、Sr、La、Ga、Mg、Gd、Sm、Ca、Ce、Fe、Al、Ta、Mo、Sc、V、Zn、Cu、In、S、B、Ge、Si及びBiから選ばれる少なくともいずれか一つ以上である。)
[化2]LiaM2bOc
前記化学式2において、前記0<a≦4、0<b≦5及び0<c≦12であり、M2は、Ti、Al及びZrから選ばれる少なくともいずれか一つ以上であり得る。
[化3]LiaM3Ob
(前記0<a≦8、0<b≦15であり、M3は、Na、K、Mg、Al、Fe、Cr、Y、Sn、Ti、B、P、Zr、Ru、Nb、W、Ba、Sr、La、Ga、Mg、Gd、Sm、Ca、Ce、Fe、Al、Ta、Mo、Sc、V、Zn、Cu、In、S、B、Ge、Si及びBiから選ばれる少なくともいずれか一つ以上である。)
共浸法(co-precipitation method)を用いて球状のNi0.2Co0.1Mn0.7CO3前駆体を合成した。90L級の反応器でNiSO4・6H2O、CoSO4・7H2O、及びMnSO4・H2Oを20:10:70のモル比(mole ratio)で混合した2.5Mの複合遷移金属硫酸水溶液に25wt%のNaCO3と28wt%のNH4OHを投入した。このとき、反応器内のpHは10.0~12.0に維持し、温度は45℃~50℃に維持した。また、不活性ガスであるN2を反応器に投入し、製造された前駆体が酸化されることを防止した。
前記製造された前駆体をBox焼成炉でO2又は空気(50L/min)雰囲気に維持し、1分当たり2℃に昇温し、550℃で1時間~6時間維持した後、炉冷(furnace cooling)した。
前記焙焼された前駆体に対して、Li/(Ni+Co+Mn)の比率が1.45になるようにLiOH又はLi2CO3を秤量し、融剤ドーパント(Flux dopant)としてNb2O5を0.6モル%秤量し、これらをミキサー(Manual mixer、MM)を用いて混合した。
表面処理用ドーパントとしてTiO2 1.0モル%を秤量し、これをミキサー(Manual mixer、MM)を用いて混合した。
前記実施例1のコーティング段階において、表面処理ドーパントとしてAl2O3 1.0モル%を混合することを除いては、前記実施例1と同一の方法で正極活物質を製造した。
前記実施例1のコーティング段階において、表面処理ドーパントとしてn-ZrO2 1.0モル%を混合することを除いては、前記実施例1と同一の方法で正極活物質を製造した。
前記実施例1のコーティング段階において、表面処理ドーパントとしてTiO2 0.19モル%,Al2O3 0.77モル%、及びn-ZrO2 0.04モル%を混合することを除いては、前記実施例1と同一の方法で正極活物質を製造した。
前記実施例1で融剤ドーパント(Flux dopant)を混合せず、コーティング段階を行わないことを除いては、前記実施例1と同一の方法で正極活物質を製造した。
前記実施例1でコーティング段階を行わないことを除いては、前記実施例1と同一の方法で正極活物質を製造した。
前記実施例及び比較例に係る正極活物質90重量%、カーボンブラック5.5wt%、PVDFバインダー4.5wt%をN-メチル-2ピロリドン(NMP)30gに分散させ、正極スラリーを製造した。前記正極スラリーを厚さ15μmの正極集電体であるアルミニウム(Al)薄膜に塗布及び乾燥し、ロールプレス(roll press)を実施することによって正極を製造した。正極のローディングレベルは5.5mg/cm2であり、電極密度は2.3g/cm3であった。
図1を参照すると、前記実施例1~3に係る正極活物質の表面にTi、Al及びZrコーティング層が均一に分布することを確認することができる。
Claims (15)
- 下記の化学式1で表されるリチウム過剰層状酸化物;及び
前記化学式1で表されるリチウム過剰層状酸化物の表面に形成されたイオン伝導性コーティング層;を含む、二次電池用正極活物質。
[化1]rLi2MnO3・(1-r)LiaNixCoyMnzM11-(x+y+z)O2
(前記化学式1において、0<r≦0.6、0<a≦1、0≦x≦1、0≦y<1、0≦z<1、及び0<x+y+z≦1であり、前記M1は、Na、K、Mg、Al、Fe、Cr、Y、Sn、Ti、B、P、Zr、Ru、Nb、W、Ba、Sr、La、Ga、Mg、Gd、Sm、Ca、Ce、Fe、Al、Ta、Mo、Sc、V、Zn、Cu、In、S、B、Ge、Si及びBiから選ばれる少なくともいずれか一つ以上である。) - 前記イオン伝導性コーティング層は、Ti、Al及びZrから選ばれる少なくともいずれか一つ以上を含む、請求項1に記載の二次電池用正極活物質。
- 前記イオン伝導性コーティング層は、下記の化学式2で表される物質を含む、請求項1に記載の二次電池用正極活物質。
[化2]LiaM2bOc
(前記0<a≦4、0<b≦5及び0<c≦12であり、M2は、Ti、Al及びZrから選ばれる少なくともいずれか一つ以上である。) - 前記イオン伝導性コーティング層は、前記リチウム過剰層状酸化物に対して0.05モル%~5.0モル%の含量で含まれる、請求項1に記載の二次電池用正極活物質。
- 前記イオン伝導性コーティング層の厚さは1nm~100nmである、請求項1に記載の二次電池用正極活物質。
- 前記正極活物質は、1次粒子が凝集することによって2次粒子を形成し、
大きさが300nm~10μmである1次粒子が前記2次粒子を構成する1次粒子中に50vol%~100vol%に調節される、請求項1に記載の二次電池用正極活物質。 - 前記化学式1の前記M1は、前記1次粒子を成長させる融剤(Flux)として作用するドーパントである、請求項1に記載の二次電池用正極活物質。
- 前記化学式1の前記M1は、Ba、Sr、B、P、Y、Zr、Nb、Mo、Ta及びWから選ばれる少なくともいずれか一つ以上である、請求項1に記載の二次電池用正極活物質。
- 前記化学式1の前記M1は、前記リチウム過剰層状酸化物全体の金属のモル数に対して0.001モル%~10モル%で含まれる、請求項1に記載の二次電池用正極活物質。
- 前記化学式1で表されるリチウム過剰層状酸化物に含まれるNi、Co、又はMnの全体の金属のモル数に対するリチウムのモル数の比率(Li/Ni+Co+Mn)は、1.1~1.6である、請求項1に記載の二次電池用正極活物質。
- 前記化学式1で表されるリチウム過剰層状酸化物において、Ni全体のモル数に対するMnのモル数の比率(Mn/Ni)は、1~4.5である、請求項1に記載の二次電池用正極活物質。
- 請求項1の二次電池用正極活物質を製造する方法において、
正極活物質前駆体を製造する第1段階;
前記正極活物質前駆体にリチウム化合物を混合して焼成し、リチウム複合酸化物を形成する第2段階;及び
前記第2段階で形成されたリチウム複合酸化物とコーティング前駆体とを混合し、イオン伝導性コーティング層を形成する第3段階;を含む、二次電池用正極活物質の製造方法。 - 前記第2段階は、前記化学式1のM1を含む化合物をさらに混合して焼成する、請求項12に記載の二次電池用正極活物質の製造方法。
- 前記コーティング前駆体は、TiO2、Al2O3、Al(OH)3、ZrO2、及びZr(OH)4から選ばれる少なくともいずれか一つ以上である、請求項12に記載の二次電池用正極活物質の製造方法。
- 請求項1の正極活物質を含む二次電池。
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KR1020200135029A KR102558594B1 (ko) | 2019-10-18 | 2020-10-19 | 리튬 이차전지 양극활물질, 이의 제조방법, 및 이를 포함하는 리튬 이차전지 |
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JP2012190772A (ja) * | 2011-02-25 | 2012-10-04 | Idemitsu Kosan Co Ltd | 全固体リチウムイオン電池及び正極合材 |
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JP2014222607A (ja) * | 2013-05-13 | 2014-11-27 | 日産自動車株式会社 | 固溶体活物質を含む正極活物質、該正極活物質を含む正極、および該正極を用いた非水電解質二次電池 |
JP2015099646A (ja) * | 2013-11-18 | 2015-05-28 | 株式会社Gsユアサ | リチウム二次電池用正極活物質、リチウム二次電池用電極、リチウム二次電池 |
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JP2012190772A (ja) * | 2011-02-25 | 2012-10-04 | Idemitsu Kosan Co Ltd | 全固体リチウムイオン電池及び正極合材 |
JP2014041720A (ja) * | 2012-08-21 | 2014-03-06 | Idemitsu Kosan Co Ltd | 全固体リチウムイオン電池及び正極合材 |
JP2014222607A (ja) * | 2013-05-13 | 2014-11-27 | 日産自動車株式会社 | 固溶体活物質を含む正極活物質、該正極活物質を含む正極、および該正極を用いた非水電解質二次電池 |
JP2015099646A (ja) * | 2013-11-18 | 2015-05-28 | 株式会社Gsユアサ | リチウム二次電池用正極活物質、リチウム二次電池用電極、リチウム二次電池 |
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