JP7470455B2 - ハイエントロピー正極材料、その製造方法および応用 - Google Patents
ハイエントロピー正極材料、その製造方法および応用 Download PDFInfo
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- JP7470455B2 JP7470455B2 JP2022511376A JP2022511376A JP7470455B2 JP 7470455 B2 JP7470455 B2 JP 7470455B2 JP 2022511376 A JP2022511376 A JP 2022511376A JP 2022511376 A JP2022511376 A JP 2022511376A JP 7470455 B2 JP7470455 B2 JP 7470455B2
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- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims description 83
- 238000004519 manufacturing process Methods 0.000 title description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 52
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 27
- 238000000975 co-precipitation Methods 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 239000007773 negative electrode material Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 claims description 3
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002733 tin-carbon composite material Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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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- 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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Description
本願は、発明の名称が「ハイエントロピー正極材料、その製造方法および応用」である、2021年2月10日に中国特許庁へ提出された中国特許出願202110183314.Xに基づく優先権を主張し、その全内容は、援用により本明細書に組み込まれる。
Li1+aAxByCzDbO2McNd 式(I)
(式(I)中、Aは+2価金属元素であり、Bは+3価金属元素であり、Cは+4価金属元素であり、Dは+5価金属元素であり、Mは+7価元素であり、Nは+8価元素であり、0≦a<1、0<x<1、0<y<1、0<z<1、0<b<1、0<c<1、d>0)
a)共沈殿によりA、B、C、D、Mの一種又は複数種を含有する前駆体を合成するステップと、
b)ステップa)で得られた前駆体をリチウムと混合し、同時にA、B、C、D、Mの一種又は複数種を含有する酸化物を加えて混合した後、焼結し、Li1+aAxByCzDbO2McNdで表されるハイエントロピーリチウム電池正極材料の中間体を得るステップと、
c)ステップb)で得られたLi1+aAxByCzDbO2McNdで表されるハイエントロピーリチウム電池正極材料の中間体を表面処理し、コーティングし、ハイエントロピー正極材料を得るステップと、を含む製造方法、を提供する。
Li1+aAxByCzDbO2McNd 式(I)
(式(I)中、Aは+2価金属元素であり、Bは+3価金属元素であり、Cは+4価金属元素であり、Dは+5価金属元素であり、Mは+7価元素であり、Nは+8価元素であり、0≦a<1、0<x<1、0<y<1、0<z<1、0<b<1、0<c<1、d>0)
a)共沈殿によりA、B、C、D、Mの一種又は複数種を含有する前駆体を合成するステップと、
b)ステップa)で得られた前駆体をリチウムと混合し、同時にA、B、C、D、Mの一種又は複数種を含有する酸化物を加えて混合した後、焼結し、Li1+aAxByCzDbO2McNdで表されるハイエントロピーリチウム電池正極材料の中間体を得るステップと、
c)ステップb)で得られたLi1+aAxByCzDbO2McNdで表されるハイエントロピーリチウム電池正極材料の中間体を表面処理し、コーティングし、ハイエントロピー正極材料を得るステップとを含むハイエントロピー正極材料の製造方法、を提供する。
(1)共沈法によりNi0.08Co0.08Al0.08Ti0.08Mn0.6(OH)2で表される前駆体を合成し、モル比8:8:8:8:60の割合で、モル濃度2mol/LのNiSO4と、CoSO4と、NaAlO2と、チタン酸テトラブチルと、MnSO4との混合溶液を調製し、モル濃度1.2mol/Lのアンモニア水溶液を調製し、モル濃度5mol/Lの水酸化ナトリウム溶液を調製し、体積比2:0.5:1で、用意された混合溶液、アンモニア水溶液、水酸化ナトリウム溶液をそれぞれ反応釜に投入し、共沈殿反応を行い、反応中に反応釜の温度を55℃に制御し、反応系のpHを11.3程度に制御し、20時間反応させた後、Ni0.08Co0.08Al0.08Ti0.08Mn0.6(OH)2の懸濁液を得た。Ni0.08Co0.08Al0.08Ti0.08Mn0.6(OH)2の懸濁液を45℃の温水で洗浄し、100℃で10時間乾燥させた後、Ni0.08Co0.08Al0.08Ti0.08Mn0.6(OH)2で表される前躯体を得た。
(1)共沈法によりNi0.1Co0.1Mn0.4(OH)2で表される前駆体を合成し、モル比1:1:4の割合で、モル濃度2mol/LのNiSO4と、CoSO4と、MnSO4との混合溶液を調製し、モル濃度1.2mol/Lのアンモニア水溶液を調製し、モル濃度4mol/Lの水酸化ナトリウム溶液を調製し、体積比2:2:1.5で、用意された混合溶液、アンモニア水溶液、水酸化ナトリウム溶液をそれぞれ反応釜に投入し、共沈殿反応を行い、反応中に反応釜の温度を65℃に制御し、反応系のpHを11.45程度に制御し、28時間反応させた後、Ni0.1Co0.1Mn0.4(OH)2の懸濁液を得た。Ni0.1Co0.1Mn0.4(OH)2の懸濁液を50℃の温水で洗浄し、120℃で12時間乾燥させた後、Ni0.1Co0.1Mn0.4(OH)2前躯体を得た。
(1)共沈法によりNi0.1Co0.1Mn0.4(OH)2で表される前駆体を合成し、モル比1:1:4の割合で、モル濃度2mol/LのNiSO4と、CoSO4と、MnSO4との混合溶液を調製し、モル濃度1.2mol/Lのアンモニア水溶液を調製し、モル濃度4mol/Lの水酸化ナトリウム溶液を調製し、体積比2:2:1.5で、用意された混合溶液、アンモニア水溶液、水酸化ナトリウム溶液をそれぞれ反応釜に投入し、共沈殿反応を行い、反応中に反応釜の温度を62℃に制御し、反応系のpHを11.45程度に制御し、55時間反応させた後、Ni0.1Co0.1Mn0.4(OH)2の懸濁液を得た。Ni0.1Co0.1Mn0.4(OH)2の懸濁液を45℃の温水で洗浄し、110℃で10時間乾燥させた後、Ni0.1Co0.1Mn0.4(OH)2で表される前躯体を得た。
Claims (3)
- 下記式(I)に示される一般式を有する、ことを特徴とするハイエントロピー正極材料であって、
Li1+aAxByCzDbO2McNd 式(I)
(式(I)中、Aは+2価金属元素であり、Bは+3価金属元素であり、Cは+4価金属元素であり、Dは+5価金属元素であり、Mは+7価元素であり、Nは+8価元素であり、0≦a<1、0<x<1、0<y<1、0<z<1、0<b<1、0<c<1、d>0)
前記+2価金属元素はNi、または、NiおよびMgであり、前記+3価金属元素はCoおよびAlであり、前記+4価金属元素はMnおよびTi、または、MnおよびZrであり、前記+5価金属元素はNbであり、前記+7価元素はFであり、前記+8価元素は格子酸素であり、
前記ハイエントロピー正極材料に含まれる酸素元素は、+6価酸素および+8価酸素の双方を持ち、
次のa)~c)のステップを含む方法で製造されることを特徴とするハイエントロピー正極材料。
a)共沈殿により合成された懸濁液を40℃~60℃の温水で洗浄し、90℃~130℃で8~14時間乾燥させ、前記A、前記B、前記C、前記D及び前記Mの一種又は複数種を含有する前駆体を得るステップであって、前記共沈殿の反応温度が50℃~70℃であり、pHが11~12であり、反応時間が15h~60hである、ステップと、
b)ステップa)で得られた前記前駆体とリチウムを含む化合物と混合し、同時に前記A、前記B、前記C、前記D及び前記Mの一種又は複数種を含有する酸化物を加えて混合した後、温度700℃~900℃、時間10h~20hの条件で焼結し、前記ハイエントロピー正極材料の中間体を得るステップと、
c)ステップb)で得られた前記ハイエントロピー正極材料の中間体を表面処理し、アルミナによりコーティングし、前記式(I)で表される前記ハイエントロピー正極材料を得るステップ。 - 正極材料、負極材料および電解質を含む高比エネルギーリチウム電池であって、
前記正極材料が請求項1に記載のハイエントロピー正極材料である、ことを特徴とする高比エネルギーリチウム電池。 - 前記負極材料は、黒鉛、シリコンカーボン材料、スズカーボン材料、赤リン、チタン酸リチウム、白リン、リチウム金属負極およびリチウムカーボン負極材料のうちの一種又は複数種を含む、ことを特徴とする請求項2に記載の高比エネルギーリチウム電池。
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