WO2023155215A1 - 正极材料及其制备方法、锂离子电池 - Google Patents
正极材料及其制备方法、锂离子电池 Download PDFInfo
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- WO2023155215A1 WO2023155215A1 PCT/CN2022/077289 CN2022077289W WO2023155215A1 WO 2023155215 A1 WO2023155215 A1 WO 2023155215A1 CN 2022077289 W CN2022077289 W CN 2022077289W WO 2023155215 A1 WO2023155215 A1 WO 2023155215A1
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- coating layer
- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 174
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000011247 coating layer Substances 0.000 claims abstract description 144
- 239000011163 secondary particle Substances 0.000 claims abstract description 102
- 239000011164 primary particle Substances 0.000 claims abstract description 86
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 69
- 239000010452 phosphate Substances 0.000 claims abstract description 69
- -1 phosphate compound Chemical class 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 42
- 239000011574 phosphorus Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000013543 active substance Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 60
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 229910001463 metal phosphate Chemical class 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 239000010406 cathode material Substances 0.000 claims description 20
- 150000002642 lithium compounds Chemical class 0.000 claims description 20
- 238000005253 cladding Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 229910052788 barium Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 10
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 8
- 150000003016 phosphoric acids Chemical class 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 235000011180 diphosphates Nutrition 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 229940048084 pyrophosphate Drugs 0.000 claims description 6
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052789 astatine Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 35
- 239000000047 product Substances 0.000 description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 29
- 239000003792 electrolyte Substances 0.000 description 11
- 239000011149 active material Substances 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 230000007774 longterm Effects 0.000 description 9
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015355 LiMgPO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 241001302239 Mycobacterium tuberculosis complex Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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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Abstract
Description
Claims (10)
- 一种正极材料,其特征在于,所述正极材料包括:二次粒子,所述二次粒子包括多个一次粒子,所述一次粒子包含活性物质,所述活性物质的化学通式为Li bNi xCo yM zR wO 2,其中,0.95≤b≤1.10,0.8≤x<1,0<y+z+w≤0.2,x+y+z+w=1,0.0001≤w≤0.003;M选自Mn及Al中的至少一种;R为掺杂金属;及包覆层,所述包覆层包括第一包覆层和第二包覆层,所述第一包覆层形成于所述一次粒子的表面,所述第二包覆层形成于所述二次粒子的表面,所述第一包覆层和第二包覆层均包含磷酸化合物;所述正极材料表面的任意一点处的单点磷含量a’,与所述正极材料表面的平均磷含量a之间满足以下关系:0.9a≤a’≤1.1a;其中,a’和a通过以下测试方法获得:在用扫描电子显微镜观察所述正极材料的情况下,对所述正极材料表面的任意一点进行EDS点扫描测试磷含量,得到a’,对扫描电子显微镜的视野中任意选取的边长为100μm的四边形区域进行EDS面扫描测试磷含量,得到a。
- 根据权利要求1所述的正极材料,其特征在于,所述Li bNi xCo yM zR wO 2中的R包括Co、Mn、Al、Ti、Zr、Sr、Mg、Ca、Y、Ba、Cu、W、Nb、La、Ce、Mo及Sn中的至少一种。
- 根据权利要求1或2所述的正极材料,其特征在于,其满足以下条件a~k的至少一者:a.所述二次粒子呈球形或者类球形;b.所述一次粒子的平均粒径为200nm~1000nm,所述二次粒子的平均粒径为3μm~20μm;c.所述磷酸化合物包括Li 3PO 4及LiR k(PO 4) r中的至少一种,0<k≤2,0<r≤2,R包括Co、Mn、Al、Ti、Zr、Sr、Mg、Ca、Y、Ba、Cu、W、Nb、La、Ce、Mo及Sn中的至少一种;d.所述第一包覆层的磷酸化合物的制备原料包括磷酸金属盐和锂化合物,所述第二包覆层的磷酸化合物的制备原料包括磷酸、偏磷酸、亚磷酸、偏亚磷酸、焦磷酸、次磷酸、可溶性磷酸盐、可溶性偏磷酸盐、可溶性亚磷酸盐、可溶性偏亚磷酸盐、可溶性焦磷酸盐和可溶性次磷酸盐中的至少一种;e.所述第一包覆层中的磷酸化合物的磷酸根含量为所述二次粒子的总质量的0.03wt%~0.3wt%;f.所述第二包覆层中的磷酸化合物的磷酸根含量为所述二次粒子和所述第一包覆层的总质量的0.1wt%~0.7wt%;g.所述第一包覆层或所述第二包覆层中的磷酸化合物的晶化磷酸根含量为磷酸根总质量的5wt%~50wt%;h.所述第一包覆层的厚度为0.005μm~0.05μm;i.所述第二包覆层的厚度为0.02μm~0.2μm;j.所述正极材料在4kN/cm 2加压下的粉体电导率大于0.02S/cm;k.所述正极材料的比表面积为0.2m 2/g~2.0m 2/g。
- 一种正极材料的制备方法,其特征在于,所述方法包括以下步骤:将Ni aCo bM cO或Ni aCo bM c(OH) 2、锂化合物以及磷酸金属盐混合,得到混合物,将所述混合物烧结,得到烧结物,其中,a+b+c=1,0.8≤a<1,0<b+c≤0.2,M选自Mn或Al中的至少一种,所述烧结物包括多个一次粒子及形成所述一次粒子表面的第一包覆层,所述第一包覆层包含磷酸化合物,所述磷酸金属盐的平均粒径小于0.5μm;及将所述烧结物在50℃以下(包含50℃)通过溶剂洗涤、干燥,得到所述正极材料,其中,所述正极材料包括二次粒子及形成所述二次粒子表面的第二包覆层,所述二次粒子是一次粒子的聚集体,所述第二包覆层包含磷酸化合物。
- 根据权利要求4所述的制备方法,其特征在于,其满足以下条件a~f的至少一者:a.所述锂化合物的添加量为:使得Ni、Co、M及所述磷酸金属盐中金属元素的摩尔含量总和与Li的摩尔含量比值为1:(0.95~1.10);b.所述锂化合物包括碳酸锂、氢氧化锂、醋酸锂、硝酸锂及草酸锂中的至少一种;c.所述磷酸金属盐的金属元素选自Co、Mn、Al、Ti、Zr、Sr、Mg、Ca、Y、Ba、Cu、W、Nb、La、Ce、Mo及Sn中的至少一种;d.所述磷酸金属盐中的磷酸根含量为所述混合物总质量的0.03wt%~0.3wt%;e.得到所述混合物的混合条件为:在10℃~50℃下固相混合0.3h~2h;f.得到所述烧结物的烧结条件为:于含氧气氛下于650℃~850℃烧结6h~20h。
- 根据权利要求4所述的制备方法,其特征在于,其满足以下条件a~b的至少一者:a.所述溶剂包括水和非水物质,所述非水物质包括磷酸、偏磷酸、亚磷酸、偏亚磷酸、焦磷酸、次磷酸、可溶性磷酸盐、可溶性偏磷酸盐、可溶性亚磷酸盐、可溶性偏亚磷酸盐、可溶性焦磷酸盐和可溶性次磷酸盐中的至少一种;b.所述溶剂中的磷酸根含量为所述烧结物总质量的0.1wt%~0.7wt%。
- 根据权利要求4或6所述的制备方法,其特征在于,其满足以下条件a~f的至少一者:a.所述洗涤的温度为10℃~50℃;b.由所述烧结物和所述溶剂组成的浆料浓度(烧结物(g)/溶剂(L))为500g/L~2000g/L;c.所述洗涤时间为10min~120min;d.所述干燥是在氮气气氛条件下进行;e.所述干燥的温度为80℃~200℃;f.所述干燥的时间为5h~48h。
- 根据权利要求4所述的制备方法,其特征在于,在将所述烧结物通过溶剂洗涤、干燥之后,所述方法还包括:将洗涤、干燥后的所述烧结物置于含氧气氛下于150℃~600℃热处理4h~10h,得到所述正极材料。
- 根据权利要求4所述的制备方法,其特征在于,其满足以下条件a~f的至少一 者:a.所述磷酸金属盐与所述锂化合物高温反应形成所述一次粒子的第一包覆层;b.所述溶剂中的磷酸根离子与所述烧结物表面残余锂反应形成所述二次粒子的第二包覆层;c.所述磷酸化合物包括Li 3PO 4及LiR k(PO 4) r中的至少一种,0<k≤2,0<r≤2,R选自Co、Mn、Al、Ti、Zr、Sr、Mg、Ca、Y、Ba、Cu、W、Nb、La、Ce、Mo、Sn中的至少一种;d.所述第一包覆层或所述第二包覆层中的磷酸化合物的晶化磷酸根含量为磷酸根总质量的5wt%~50wt%;e.所述一次粒子的平均粒径为200nm~1000nm,所述第一包覆层的厚度为0.005μm~0.05μm;f.所述二次粒子的平均粒径为3μm~20μm,所述第二包覆层的厚度为0.02~0.2μm。
- 一种锂离子电池,其特征在于,包括如权利要求1-3任一项所述正极材料或如权利要求4~9任一项所述正极材料的制备方法制备的正极材料。
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