CN107968201A - 一种锂离子电池正极材料及其前驱体的制备方法 - Google Patents
一种锂离子电池正极材料及其前驱体的制备方法 Download PDFInfo
- Publication number
- CN107968201A CN107968201A CN201611256094.4A CN201611256094A CN107968201A CN 107968201 A CN107968201 A CN 107968201A CN 201611256094 A CN201611256094 A CN 201611256094A CN 107968201 A CN107968201 A CN 107968201A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ion batteries
- anode material
- preparation
- presoma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 239000010405 anode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000004411 aluminium Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000012670 alkaline solution Substances 0.000 claims abstract description 22
- 238000009938 salting Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012391 LiCo0.99Al0.01O2 Inorganic materials 0.000 description 1
- 229910016191 LiNi0.9Al0.1O2 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 washing Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/36—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
- H01M4/50—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/36—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明提供了一种锂离子电池正极材料及其前驱体的制备方法。将盐溶液、含有铝元素、氨水的碱性溶液一起并流加入到带溢流口的反应釜中进行反应,溢流得到的前驱体浆料经过固液分离、洗涤、烘干、筛分,得到均匀掺铝的前驱体,然后将该前驱体与锂源混合、烧结、破碎、筛分,得到均匀掺铝的正极材料。该方法能够实现铝元素的均匀掺杂,并且工艺简单,过程容易稳定控制,生产成本低,适于大规模工业化生产。
Description
技术领域
本发明涉及一种锂离子电池正极材料及其前驱体的制备方法,具体来讲涉及一种掺铝的锂离子电池正极材料及其前驱体的制备方法。
背景技术
锂离子电池是绿色高能电池,具有电压高、能量密度大、循环性能好、自放电小、无记忆效应等突出优点,广泛应用于各种便携式电动工具、电子仪表、移动电话、笔记本电脑、摄录机、武器装备等,在电动汽车以及各类储能领域也已经大规模使用。
近年来,锂离子电池的产量飞速增长,应用领域不断扩大,市场对锂离子电池能量密度的要求越来越高,相应的需要不断提高锂离子电池正极材料的能量密度,但随着材料能量密度的提高,其循环性能、安全性能随之下降,如何在不牺牲容量的情况下,同时改进其循环和安全性能,成为亟待解决的问题。
目前提高锂离子电池正极材料循环和安全性能的主要改性方法是掺杂和包覆,其中掺杂铝元素可以稳定材料结构,明显抑制充放电过程中的放热反应,能够有效的改善正极材料循环和安全性能。在化学共沉淀合成掺铝的正极材料前驱体时,由于镍钴锰元素与铝元素的沉淀pH差异较大,溶度积常数最大相差1018倍,同时三价铝很难与氨水发生络合,所以采用常规的液相共沉淀法,铝极易生成絮状产物,导致掺铝前驱体中铝元素分布不均匀,同时常规的液相共沉淀法通常将镍钴锰等盐溶液、铝盐溶液、碱溶液、络合剂溶液分别加入反应釜进行反应,不但过程控制难度大,产品指标稳定性差,而且设备投入多,成本高。
发明内容
本发明提供的一种锂离子电池正极材料及其前驱体的制备方法,该方法能够实现铝元素的均匀掺杂,产品性能得到了明显提升,并且工艺简单,过程控制容易,能够比较容易地控制反应体系和产品指标的稳定性,生产成本低,更适于大规模工业化生产。
本发明的技术方案如下:
一种锂离子电池正极材料及其前驱体的制备方法,包括如下步骤:
(1)将含有Ni、Co、Mn元素的一种或几种的金属盐配制成浓度为1-3mol/L的盐溶液,将铝盐、碱、氨水按一定比例混合配制成浓度为2-10mol/L的碱性溶液;
(2)将步骤(1)中的盐溶液、碱性溶液溶液一起并流加入到带溢流口的反应釜中进行反应,过程保持搅拌,同时控制盐溶液与碱性溶液的进液流量,反应温度为40-70℃,溢流得到的前驱体浆料经过固液分离、洗涤、烘干、筛分后,得到均匀掺铝的球形前驱体;
(3)将步骤(2)中得到的前驱体与锂源混合,在空气或氧气气氛中,700-1150℃下烧结4-20h,经过破碎、筛分,得到锂离子电池正极材料。
上述制备方法中,所述的锂离子电池正极材料通式为:
LiNixCoyMnzAldO2
其中,0≤x<1,0≤y<1,0≤z<1,0.001≤d≤0.1,x+y+z+d=1。
上述制备方法中,所述的前驱体通式为:
NixCoyMnzAld(OH)2+d
其中,0≤x<1,0≤y<1,0≤z<1,0.001≤d≤0.1,x+y+z+d=1。
上述制备方法中,步骤(1)中所述的金属盐为硫酸盐、氯化盐、硝酸盐、醋酸盐中的一种或其中几种。
上述制备方法中,步骤(1)中所述铝盐为硫酸铝、硝酸铝、氯化铝中的一种或其中几种。
上述制备方法中,步骤(1)中所述碱为氢氧化钠、氢氧化钾中的一种或两种。
上述制备方法中,步骤(2)反应过程可以向反应釜里通入氮气。
上述制备方法中,步骤(3)中所述的锂源为碳酸锂、氢氧化锂和硝酸锂中的一种或其中几种。
本发明具有下述优点:
与现有技术相比,本发明先将铝盐与氢氧化钠、氨水混合配制成一定浓度的含铝碱性溶液。一方面反应过程中铝元素沉淀速度减慢,从而与镍钴锰元素实现均匀共沉淀;另一方面反应过程仅需控制盐溶液与碱性溶液这两种溶液的进液流量,工艺简单,能够比较容易的控制反应体系和产品指标的稳定性,从而实现产品的连续稳定生产。
附图说明
图1 为本发明实施例1所制一种锂离子电池正极材料前驱体的扫描电子显微镜(SEM)图。
图2 为本发明实施例1所制一种锂离子电池正极材料前驱体颗粒剖面的元素线扫描电子显微镜(SEM)图。
图3为本发明实施例1所制一种锂离子电池正极材料前驱体中铝元素的能谱分析(EDS)图。
图4为本发明实施例1所制一种锂离子电池正极材料的扫描电子显微镜(SEM)图。
具体实施方式
通过下述实施例及附图将有助于理解本发明,但不限制本发明的内容。
实施例1
将硫酸镍、硫酸钴按照金属摩尔比87:10的比例溶解得到2mol/L的混合盐溶液;将硝酸铝、氢氧化钠、氨水按照摩尔比3:204:50的比例溶解得到4mol/L的碱性溶液。盐溶液、碱性溶液分别放入不同容器中,并将两种溶液一起并流加入到带溢流口的反应釜中,过程保持搅拌,控制反应体系的盐溶液流量为0.97L/h,碱性溶液流量为1.29L/h,反应温度为50℃,连续溢流得到的前驱体浆料经过压滤机固液分离、洗涤,滤饼105℃烘干10h后筛分,得到均匀掺铝的球形前驱体。将上述前驱体材料与氢氧化锂混合配料,在氧气气氛中,760℃烧结12h,经过破碎、筛分,得到锂离子电池正极材料LiNi0.87Co0.1Al0.03O2。
实施例2
将硝酸镍、硫酸钴、氯化锰按照金属摩尔比80:10:9的比例溶解得到1mol/L的混合盐溶液;将氯化铝、氢氧化钠、氨水按照摩尔比1:203:35的比例溶解得到6mol/L的碱性溶液。盐溶液、碱性溶液分别放入不同容器中,并将两种溶液一起并流加入到带溢流口的反应釜中,在N2气氛保护下进行反应,过程保持搅拌,控制反应体系的盐溶液流量为1.98L/h,碱性溶液流量为0.8L/h,反应温度为55℃,连续溢流得到的前驱体浆料经过压滤机固液分离、洗涤,滤饼115℃烘干5h后筛分,得到均匀掺铝的球形前驱体。将上述前驱体材料与氢氧化锂混合配料,在氧气气氛中,760℃烧结10h,经过破碎、筛分,得到锂离子电池正极材料LiNi0.8Co0.1 Mn0.09Al0.01O2。
实施例3
将硫酸镍溶解得到2.5mol/L的盐溶液;将硫酸铝、氢氧化钠、氨水按照摩尔比5:105:30的比例溶解得到8mol/L的碱性溶液。盐溶液、碱性溶液分别放入不同容器中,并将两种溶液一起并流加入到带溢流口的反应釜中,过程保持搅拌,控制反应体系的盐溶液流量为1.8L/h,碱性溶液流量为1.75L/h,反应温度为50℃,连续溢流得到的前驱体浆料经过压滤机固液分离、洗涤,滤饼115℃烘干5h后筛分,得到均匀掺铝的球形前驱体。将上述前驱体材料与氢氧化锂混合配料,在氧气气氛中,740℃烧结15h,经过破碎、筛分,得到锂离子电池正极材料LiNi0.9Al0.1O2。
实施例4
将氯化镍、硫酸锰按照金属摩尔比49:49的比例溶解得到3mol/L的混合盐溶液;将硝酸铝、氢氧化钠、氨水按照摩尔比1:101:12的比例溶解得到10mol/L的碱性溶液。盐溶液、碱性溶液分别放入不同容器中,并将两种溶液一起并流加入到带溢流口的反应釜中,在N2气氛保护下进行反应,过程保持搅拌,控制反应体系的盐溶液流量为0.98L/h,碱性溶液流量为0.68L/h,反应温度为45℃,连续溢流得到的前驱体浆料经过离心机固液分离、洗涤,滤饼120℃烘干5h后筛分,得到均匀掺铝的球形前驱体。将上述前驱体材料与碳酸锂混合配料,在空气气氛中,890℃烧结14h,经过破碎、筛分,得到锂离子电池正极材料LiNi0.49Mn0.49Al0.02O2。
实施例5
将醋酸镍、醋酸钴、醋酸锰按照金属摩尔比60:19.8:19.8的比例溶解得到1.5mol/L的混合盐溶液;将硫酸铝、氢氧化钠、氨水按照摩尔比1:1010:230的比例溶解得到3mol/L的碱性溶液。盐溶液、碱性溶液分别放入不同容器中,并将两种溶液一起并流加入到带溢流口的反应釜中,在N2气氛保护下进行反应,过程保持搅拌,控制反应体系的盐溶液流量为1.992L/h,碱性溶液流量为2.48L/h,反应温度为60℃,连续溢流得到的前驱体浆料经过压滤机固液分离、洗涤,滤饼110℃烘干5h后筛分,得到均匀掺铝的球形前驱体。将上述前驱体材料与碳酸锂混合配料,在空气气氛中,850℃烧结5h,经过破碎、筛分,得到锂离子电池正极材料LiNi0.6Co0.198Mn0.198Al0.004O2。
实施例6
将氯化钴溶解得到3mol/L的盐溶液;将硝酸铝、氢氧化钠、氨水按照摩尔比1:618:90的比例溶解得到2mol/L的碱性溶液。盐溶液、碱性溶液分别放入不同容器中,并将两种溶液一起并流加入到带溢流口的反应釜中,在N2气氛保护下进行反应,过程保持搅拌,控制反应体系的盐溶液流量为2.18L/h,碱性溶液流量为7.82L/h,反应温度为65℃,连续溢流得到的前驱体浆料经过离心机固液分离、洗涤,滤饼130℃烘干6h后筛分,得到均匀掺铝的球形前驱体。将上述前驱体材料与碳酸锂混合配料,在空气气氛中,1120℃烧结14h,经过破碎、筛分,得到锂离子电池正极材料LiCo0.99Al0.01O2。
实施例7
将氯化镍、硫酸钴、硝酸锰按照金属摩尔比50:20:29.7的比例溶解得到2mol/L的混合盐溶液;将硝酸铝、氢氧化钠、氨水按照摩尔比1:700:55的比例溶解得到8mol/L的碱性溶液。盐溶液、碱性溶液分别放入不同容器中,并将两种溶液一起并流加入到带溢流口的反应釜中,在N2气氛保护下进行反应,过程保持搅拌,控制反应体系的盐溶液流量为2.28L/h,碱性溶液流量为1.295L/h,反应温度为55℃,连续溢流得到的前驱体浆料经过压滤机固液分离、洗涤,滤饼120℃烘干8h后筛分,得到均匀掺铝的球形前驱体。连将上述前驱体材料与碳酸锂混合配料,在空气气氛中,900℃烧结20h,经过破碎、筛分,得到锂离子电池正极材料LiNi0.50Co0.20Mn0.297Al0.003O2。
Claims (8)
1.一种锂离子电池正极材料及其前驱体的制备方法,包括以下步骤: (1)将含有Ni、Co、Mn元素的一种或几种的金属盐配制成浓度为1-3mol/L的盐溶液,将铝盐、碱、氨水按一定比例混合配制成浓度为2-10mol/L的碱性溶液;(2)将步骤(1)中的盐溶液、碱性溶液溶液一起并流加入到带溢流口的反应釜中进行反应,过程保持搅拌,同时控制盐溶液与碱性溶液的进液流量,反应温度为40-70℃,溢流得到的前驱体浆料经过固液分离、洗涤、烘干、筛分后,得到均匀掺铝的球形前驱体;(3)将步骤(2)中得到的前驱体与锂源混合,在空气或氧气气氛中,700-1150℃下烧结4-20h,经过破碎、筛分,得到锂离子电池正极材料。
2.根据权利要求1所述锂离子电池正极材料及其前驱体的制备方法,其特征在于所述的锂离子电池正极材料通式为:LiNixCoyMnzAldO2 其中,0≤x<1,0≤y<1,0≤z<1,0.001≤d≤0.1,x+y+z+d=1。
3.根据权利要求1所述锂离子电池正极材料及其前驱体的制备方法,其特征在于所述的锂离子电池正极材料前驱体通式为:NixCoyMnzAld(OH)2+d 其中,0≤x<1,0≤y<1,0≤z<1,0.001≤d≤0.1,x+y+z+d=1。
4.根据权利要求1所述锂离子电池正极材料及其前驱体的制备方法,其特征在于步骤(1)中所述的金属盐为硫酸盐、氯化盐、硝酸盐、醋酸盐中的一种或其中几种。
5.根据权利要求1所述锂离子电池正极材料及其前驱体的制备方法,其特征在于步骤(1)中所述的铝盐为硫酸铝、硝酸铝、氯化铝中的一种或其中几种。
6.根据权利要求1所述锂离子电池正极材料及其前驱体的制备方法,其特征在于步骤(1)中所述的碱为氢氧化钠、氢氧化钾中的一种或两种。
7.根据权利要求1所述锂离子电池正极材料及其前驱体的制备方法,其特征在于步骤(2)中在反应过程向反应釜里通入氮气。
8.根据权利要求1所述锂离子电池正极材料及其前驱体的制备方法,其特征在于步骤(3)中所述的锂源为碳酸锂、氢氧化锂和硝酸锂中的一种或其中几种。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2016109142929 | 2016-10-20 | ||
CN201610914292 | 2016-10-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107968201A true CN107968201A (zh) | 2018-04-27 |
Family
ID=61997399
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611256094.4A Pending CN107968201A (zh) | 2016-10-20 | 2016-12-30 | 一种锂离子电池正极材料及其前驱体的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107968201A (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109309229A (zh) * | 2018-12-03 | 2019-02-05 | 林奈(中国)新能源有限公司 | 一种包覆改性的高镍四元正极材料、制备方法及用途 |
CN109473657A (zh) * | 2018-12-03 | 2019-03-15 | 林奈(中国)新能源有限公司 | 一种掺杂包覆的镍钴铝锰四元锂离子电池正极材料、制备方法及用途 |
CN112047391A (zh) * | 2020-09-03 | 2020-12-08 | 浙江中金格派锂电产业股份有限公司 | 一种单晶型镍锰铝酸锂正极材料的制备方法 |
WO2023179048A1 (zh) * | 2022-03-25 | 2023-09-28 | 广东邦普循环科技有限公司 | 一种氟铝共掺杂的钴酸锂正极材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101262061A (zh) * | 2008-04-14 | 2008-09-10 | 天津巴莫科技股份有限公司 | 锂离子电池用球形掺铝镍钴酸锂及其制备方法 |
CN102569781A (zh) * | 2012-03-27 | 2012-07-11 | 天津理工大学 | 一种高电压锂离子电池正极材料及其制备方法 |
CN103178263A (zh) * | 2013-02-21 | 2013-06-26 | 湖南桑顿新能源有限公司 | 一种镍钴铝酸锂正极材料的制备方法 |
CN103553152A (zh) * | 2013-10-22 | 2014-02-05 | 金天能源材料有限公司 | 高密度球形镍钴铝前驱体材料及其制备方法 |
CN104701527A (zh) * | 2013-12-05 | 2015-06-10 | 陕西汇沣新能源科技有限公司 | 一种锂离子电池正极材料镍钴铝酸锂的制备方法 |
-
2016
- 2016-12-30 CN CN201611256094.4A patent/CN107968201A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101262061A (zh) * | 2008-04-14 | 2008-09-10 | 天津巴莫科技股份有限公司 | 锂离子电池用球形掺铝镍钴酸锂及其制备方法 |
CN102569781A (zh) * | 2012-03-27 | 2012-07-11 | 天津理工大学 | 一种高电压锂离子电池正极材料及其制备方法 |
CN103178263A (zh) * | 2013-02-21 | 2013-06-26 | 湖南桑顿新能源有限公司 | 一种镍钴铝酸锂正极材料的制备方法 |
CN103553152A (zh) * | 2013-10-22 | 2014-02-05 | 金天能源材料有限公司 | 高密度球形镍钴铝前驱体材料及其制备方法 |
CN104701527A (zh) * | 2013-12-05 | 2015-06-10 | 陕西汇沣新能源科技有限公司 | 一种锂离子电池正极材料镍钴铝酸锂的制备方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109309229A (zh) * | 2018-12-03 | 2019-02-05 | 林奈(中国)新能源有限公司 | 一种包覆改性的高镍四元正极材料、制备方法及用途 |
CN109473657A (zh) * | 2018-12-03 | 2019-03-15 | 林奈(中国)新能源有限公司 | 一种掺杂包覆的镍钴铝锰四元锂离子电池正极材料、制备方法及用途 |
CN112047391A (zh) * | 2020-09-03 | 2020-12-08 | 浙江中金格派锂电产业股份有限公司 | 一种单晶型镍锰铝酸锂正极材料的制备方法 |
WO2023179048A1 (zh) * | 2022-03-25 | 2023-09-28 | 广东邦普循环科技有限公司 | 一种氟铝共掺杂的钴酸锂正极材料及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108751265B (zh) | 一种锂离子电池正极材料及其前驱体的制备方法 | |
CN105406036B (zh) | 一种锂离子电池高电压钴酸锂正极材料及其制备方法 | |
CN103904323B (zh) | 一种球形羟基氧化钴的制备方法 | |
CN103562136B (zh) | 镍复合氢氧化物粒子和非水电解质二次电池 | |
US10074856B2 (en) | Lithium-rich manganese-based positive electrode material and preparation method therefor | |
CN111129463B (zh) | 一种mof包覆的单晶三元正极材料及其前驱体的制备方法 | |
EP3297072A1 (en) | Methods for preparing nickel-cobalt-aluminum precursor material and or positive electrode material with gradient distribution of aluminum element | |
CN106505193A (zh) | 单晶镍钴锰酸锂正极材料及其制备方法和锂离子电池 | |
CN104037404B (zh) | 一种锂离子电池用镍钴铝锂和锰酸锂复合材料及其制备方法 | |
CN106505195A (zh) | 一种高镍正极材料及其制备方法和锂离子电池 | |
CN102299299A (zh) | 锂离子电池正极材料包覆铝的制备方法 | |
CN104733724A (zh) | 高镍型锂离子二次电池正极材料及其制备方法 | |
CN102683645A (zh) | 一种锂离子电池正极材料层状富锂锰基氧化物的制备方法 | |
CN103715418A (zh) | 一种球形四氧化三钴的制备方法 | |
CN105118981A (zh) | 一种高容量镍钴锰酸锂前驱体及其制备方法 | |
CN102315429A (zh) | 锂离子电池正极材料固相法掺杂铝的制备方法 | |
CN106684351A (zh) | 一种镍钴锰三元前驱体及其制备方法 | |
CN111115662B (zh) | 一种锂电池材料回收方法 | |
CN108767216A (zh) | 具有变斜率全浓度梯度的锂离子电池正极材料及其合成方法 | |
CN107968201A (zh) | 一种锂离子电池正极材料及其前驱体的制备方法 | |
CN107123792A (zh) | 双层复合结构三元正极材料及其制备方法 | |
CN103647070B (zh) | 一种稀土钐改性三元正极材料的制备方法 | |
CN103325996A (zh) | 锂离子电池正极材料包覆铝钛的制备方法 | |
CN103619474A (zh) | 一种可用做电极活性材料的新型含氟材料 | |
CN104332624A (zh) | 一种镍钴锰酸锂材料前驱体的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180427 |