JP7376708B2 - リチウムモリブデン化合物がコーティングされたリチウム二次電池用の正極活物質及びその製造方法 - Google Patents
リチウムモリブデン化合物がコーティングされたリチウム二次電池用の正極活物質及びその製造方法 Download PDFInfo
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- JP7376708B2 JP7376708B2 JP2022523028A JP2022523028A JP7376708B2 JP 7376708 B2 JP7376708 B2 JP 7376708B2 JP 2022523028 A JP2022523028 A JP 2022523028A JP 2022523028 A JP2022523028 A JP 2022523028A JP 7376708 B2 JP7376708 B2 JP 7376708B2
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- 239000007774 positive electrode material Substances 0.000 title claims description 131
- 229910052744 lithium Inorganic materials 0.000 title claims description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 52
- MOOYSSSIVSFZQA-UHFFFAOYSA-N [Li].[Mo] Chemical compound [Li].[Mo] MOOYSSSIVSFZQA-UHFFFAOYSA-N 0.000 title claims description 41
- 239000005078 molybdenum compound Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000011247 coating layer Substances 0.000 claims description 27
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001228 spectrum Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- KRMNVGXOUQSDJW-UHFFFAOYSA-N lithium;oxomolybdenum Chemical compound [Li].[Mo]=O KRMNVGXOUQSDJW-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- -1 LiCoO 2 Chemical class 0.000 description 6
- 229910013184 LiBO Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 3
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 3
- 229910008290 Li—B Inorganic materials 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910010171 Li2MoO4 Inorganic materials 0.000 description 2
- 229910015179 MoB Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910011152 Li2BO4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical class [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Chemical group 0.000 description 1
- 239000010941 cobalt Chemical group 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/121—Borates of alkali metal
-
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- 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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- 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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Description
1次焼成された10μmサイズのNCM(88:5:7)リチウム二次電池正極活物質粉体の表面に残留するリチウムを水洗した後、H3BO3(B重量/正極活物質の重量=1,000ppm)を混合した後、300℃の酸素雰囲気で4時間のコーティング工程を行った。
1次焼成された10μmサイズのNCM(88:5:7)リチウム二次電池正極活物質粉体の表面に残留するリチウムを水洗した後、H3BO3(B重量/正極活物質の重量=1,000ppm)を混合した後、300℃酸素雰囲気で4時間コーティング工程を行った。1次焼成された5μmサイズのNCM(88:5:7)リチウム二次電池正極活物質に対しても同じコーティング工程を行い、最終的に10μmサイズのNCM正極活物質と5μmサイズのNCM正極活物質の重量比を8:2で混合した正極活物質を製造した。
1次焼成された10μmサイズのNCM(88:5:7)リチウム二次電池正極活物質粉体の表面に残留するリチウムを水洗した後、MoO3(Mo重量/正極活物質の重量=1,000ppm)とH3BO3(B重量/正極活物質の重量=500ppm)を混合した後、350℃の酸素雰囲気で4時間コーティング工程を行った。
1次焼成された10μmサイズのNCM(88:5:7)リチウム二次電池正極活物質粉体の表面に残留するリチウムを水洗した後、MoO3(Mo重量/正極活物質の重量=1,000ppm)とH3BO3(B重量/正極活物質の重量=500ppm)を混合した後、350℃の酸素雰囲気で4時間コーティング工程を行った。1次焼成された5μmサイズのNCM(88:5:7)リチウム二次電池正極活物質に対しても同じコーティング工程を行い、最終的に10μmサイズのNCM正極活物質と5μmサイズのNCM正極活物質の重量比を8:2で混合した正極活物質を製造した。
実施例1-2及び比較例1-2で製造された各々の正極活物質と、カーボンブラック導電材と、PVdFバインダーとを、N‐メチルピロリドン(NMP)溶媒中に96:2:2の重量比で混合して正極スラリーを製造し、それをアルミニウム集電体の一面に塗布した後、100℃で乾燥した後に圧延して正極を製造した。負極には、リチウムメタルを使用した。
このように製造された各リチウム二次電池ハーフセルに対し、25℃でCC‐CVモードで、0.2Cで4.25Vになるまで充電し、0.2Cの定電流で2.5Vまで放電、0.2Cで4.25Vになるまで充電して充放電実験を行った後、セルを分解して正極をDMCで5秒間洗浄した。
正極活物質、導電材、バインダー、添加剤の割合を各々、97.5/1.0/1.35/0.15にして正極スラリーを作る。アルミニウム集電体に正極スラリーをコーティングし、天然黒鉛と人造黒鉛を特定の割合で配合して対極としての負極を準備する。電解液は塩0.7Mで準備し、寿命維持のためにLiFSI(Lithium bis(fluorosulfonyl)imide,0.3M)を添加して使用する。注液量は、電極当たり100μLに算定し、自社製造の分離膜を適正な大きさで正極と負極との間に位置させる。準備されたモノセルに電解液を入れてフォーメーション(formation)を行って初期ガスを除去し、モノセルの評価を準備する。
ToF‐SIMS分析を実施してコーティング層の成分を確認した。通常、材料組成及び結晶構造の確認にはXRD測定を行うが、正極活物質のコーティング層の厚さは、数~数十nmの厚さを有するため、XRD測定ではピークの検出が容易ではない。本発明では、ToF‐SIMS分析によって非常に薄いコーティング層の成分を確認した。ToF‐SIMS分析結果、本発明の実施例において正極活物質の表面にリチウムモリブデン化合物コーティング層を確認した。即ち、本発明の製造方法によって、リチウムモリブデン化合物が形成されたことを確認した。
Claims (12)
- リチウム二次電池用の正極活物質粉体の表面にコーティング層を含み、前記コーティング層はリチウムモリブデン化合物及びリチウムホウ素化合物を含むことを特徴とする、正極活物質。
- 前記リチウムモリブデン化合物が、リチウムモリブデン酸化物であることを特徴とする、請求項1に記載の正極活物質。
- 前記リチウムモリブデン化合物は、ToF‐SIMSスペクトルにおけるピーク強度比が、LiMoO4 -:LiMoO4H2 -=1:0.2~0.8であることを特徴とする、請求項1または2に記載の正極活物質。
- 前記リチウムモリブデン化合物は、ToF‐SIMSスペクトルにおけるピーク強度比がLiMoO4 -:LiMoO13 -=1:0.03~0.3であることを特徴とする、請求項1から3のいずれか一項に記載の正極活物質。
- 前記リチウムモリブデン化合物は、ToF‐SIMSスペクトルにおけるピーク強度比が、LiMoO13 -:LiMoO13H-:LiMoO13H2 -:LiMoO13H3 -:LiMoO13H4 -=1:0.5~0.9:0.5~0.9:0.1~0.5:0.3~0.7であることを特徴とする、請求項1から4のいずれか一項に記載の正極活物質。
- 前記リチウムモリブデン化合物とホウ素が複合コーティングされていることを特徴とする、請求項1から5のいずれか一項に記載の正極活物質。
- 前記リチウム二次電池用の正極活物質粉体は、平均粒径が相異なる二種以上の正極活物質を含み、前記二種以上の正極活物質のうち平均粒径が大きい正極活物質をより多く含むことを特徴とする、請求項1から6のいずれか一項に記載の正極活物質。
- リチウム二次電池用の正極活物質粉体にMo含有ソースとB含有ソースを混合した後に熱処理することで、前記正極活物質粉体の表面にリチウムモリブデン化合物及びリチウムホウ素化合物をコーティングする段階を含む、正極活物質の製造方法。
- 前記Mo含有ソースがMoO3であり、B含有ソースがH3BO3であることを特徴とする、請求項8に記載の正極活物質の製造方法。
- 前記リチウム二次電池用の正極活物質粉体にMo含有ソースとB含有ソースを混合する前に、前記リチウム二次電池用の正極活物質粉体の表面に残留するリチウムを水洗する段階をさらに含み、水洗に際し、正極活物質:水の重量比を1:0.5~1:2にすることを特徴とする、請求項8または9に記載の正極活物質の製造方法。
- 前記Mo含有ソースとB含有ソースの量は、Mo重量/正極活物質の重量=200~5,000ppmになり、B重量/正極活物質の重量=200~2,000ppmになるようにする量であることを特徴とする、請求項8から10のいずれか一項に記載の正極活物質の製造方法。
- 前記熱処理は、空気中または酸素雰囲気で、150~800℃で行われることを特徴とする、請求項8から11のいずれか一項に記載の正極活物質の製造方法。
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