CN109678468A - 一种三元正极LiNi0.5Co0.2Mn0.3O2材料的制备及烧结方法 - Google Patents
一种三元正极LiNi0.5Co0.2Mn0.3O2材料的制备及烧结方法 Download PDFInfo
- Publication number
- CN109678468A CN109678468A CN201711010524.9A CN201711010524A CN109678468A CN 109678468 A CN109678468 A CN 109678468A CN 201711010524 A CN201711010524 A CN 201711010524A CN 109678468 A CN109678468 A CN 109678468A
- Authority
- CN
- China
- Prior art keywords
- lini
- preparation
- powder
- sintering
- target
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
-
- 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
- H01M4/50—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
-
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Abstract
一种高密度LiNi0.5Co0.2Mn0.3O2材料的制备。本发明属于非金属元素及其化合物。本发明公开了一种新的LiNi0.5Co0.2Mn0.3O2材料制备技术。把市售的LiNi0.5Co0.2Mn0.3O2粉末和成型剂PEG(聚乙二醇)经过充分混合、成型、烧结可制备出致密度超过97.1%,抗弯强度超过100MPa,显微硬度大于320HV500,电阻率小于5×10‑2Ω·cm的LiNi0.5Co0.2Mn0.3O2材料。这种LiNi0.5Co0.2Mn0.3O2材料,可制成溅射镀膜靶材,利用该种靶材通过磁控溅射镀出的LiNi0.5Co0.2Mn0.3O2正极材料制备的全固态锂离子薄膜电池,在便携式工具、太阳能电池板、数码产品、新能源电动汽车动力等领域有着广泛的应用。
Description
技术领域
本发明属于无机非金属元素及其化合物。
背景技术
三元正极材料LiNi0.5Co0.2Mn0.3O2薄膜作为新型电极材料,综合了镍酸锂,钴酸锂,锰酸锂三者的优点。LiNi0.5Co0.2Mn0.3O2材料与LiCoO2同为a-NaFeO2型层状结构,属于R3m空问,放电范围较宽(2.5~4.6eV),是目前研究的热点。三元正极LiNi0.5Co0.2Mn0.3O2薄膜热稳定性好、制备简单、价格低廉毒性相对较低,适合大规模工业化生产,有望成为新一代正极薄膜材料,替代目前使用较多的钴酸锂正极材料。以三元LiNi0.5Co0.2Mn0.3O2为正极材料制备的全固态薄膜锂电池具有更高安全系数,更高能量密度,更长循环使用寿命,广泛应用于便携式工具、数码产品、航空航天等领域,另外作为替代能源的储能装置,全固态薄膜锂电池具有更小的体积、更高的能力密度和安全性、无记忆效应直接应用于电动车及混合动力车。
LiNi0.5Co0.2Mn0.3O2材料的制备方法主要有:物理气相沉积法、共沉淀法、溶胶-凝胶法、超声喷雾热分解法、喷雾干燥法以及高温固相法等。由于物理气相沉积制备的薄膜与基体的结合强度高、沉积效率高、工艺成熟稳定而被广泛应用。而用物理气相沉积制备三元正极 LiNi0.5Co0.2Mn0.3O2薄膜需要使用高密度靶材,通过能量束轰击靶材将其气化,再沉积到基底表面形成三元正极LiNi0.5Co0.2Mn0.3O2薄膜。
发明内容
本发明公开了一种三元正极LiNi0.5Co0.2Mn0.3O2陶瓷靶材的制备工艺流程。把市售LiNi0.5Co0.2Mn0.3O2粉末,按球∶料比为10∶1,水∶料比3∶1加入去离子水制成混合料浆,湿磨72h后加入5wt%的PEG-2000溶液,继续湿磨2h后,干燥过筛,然后造粒、成型、烧结。在1100℃-1200℃温度下烧结,可制备出致密度超过97.1%,抗弯强度超过100MPa,显微硬度320HV500,电阻率小于5×10-2Ω·cm的LiNi0.5Co0.2Mn0.3O2靶材。利用三元正极LiNi0.5Co0.2Mn0.3O2薄膜制备的全固态薄膜锂电池具有充放电性能稳定、比容量大、安全性好、循环使用寿命长等优点,小到手机电池,微型用电器,大到太阳能电池板,汽车动力来源,都有着极其广泛的应用,是新一代全固态锂离子电池正极薄膜材料,有望取代传统的钴酸锂、锰酸锂正极材料,在新能源汽车动力领域,正显示出巨大的应用前景和市场。
本发明详细研究并掌握了掺杂比、球磨参数、烧结温度等对LiNi0.5Co0.2Mn0.3O2烧结致密化过程的变化规律,从而可制备出高性能的烧结LiNi0.5Co0.2Mn0.3O2材料。这种材料可经济、高效的制成各种复杂形状的产品,主要是溅射镀膜用的靶材。
附图说明
下面结合附图对本发明作进一步说明:
附图1:一种三元正极LiNi0.5Co0.2Mn0.3O2陶瓷靶材的制备工艺流程图。
下面结合附图对本发明作进一步说明:
如附图1所示,本发明的三元正极LiNi0.5Co0.2Mn0.3O2陶瓷靶材的制备工艺流程图:先将市售 LiNi0.5Co0.2Mn0.3O2粉末和成型剂加入到球磨机中于水溶液中湿磨混合,充分混合均匀后,经干燥过筛得到充分混合的LiNi0.5Co0.2Mn0.3O2粉体,然后成型(干压、冷等静压、注射成型等),得到生坯,经脱成型剂后,即可进行常压烧结,得到高强度高密度的LiNi0.5Co0.2Mn0.3O2烧结材料。
本发明的优点在于运用粉末冶金的方法,通过对LiNi0.5Co0.2Mn0.3O2粉末采用常压烧结方法,可制备出高性能的LiNi0.5Co0.2Mn0.3O2陶瓷靶材,设备成熟,工艺简单,易于大规模工业化生产,采用磁控溅射的方法镀出的LiNi0.5Co0.2Mn0.3O2膜制备出的全固态薄膜锂电池,放电比容量高,循环使用寿命长,稳定性好,安全性好,环境污染更小。
具体实施方式:
实例1:LiNi0.5Co0.2Mn0.3O2粉体的制备
将市***为99.9%LiNi0.5Co0.2Mn0.3O2粉末按质量比球∶料比10∶1混合加入5wt%聚乙二醇 (PEG),在水溶液中置于球磨机中湿磨48-72h,干燥过筛后,得到各种粉料充分混合、粒径分布均匀、成型性好LiNi0.5Co0.2Mn0.3O2粉体。
实例2:LiNi0.5Co0.2Mn0.3O2粉体1000℃烧结
将制备的LiNi0.5Co0.2Mn0.3O2粉体,在100-200MPa压力下压制成型,脱成型剂后,在高温炉内1000℃下以每分钟3度升温速率常压烧结5小时,随炉冷却。这样制得的烧结LiNi0.5Co0.2Mn0.3O2靶材,密度大于4.2g/cm3,相对密度≥91.2%,抗弯强度大于75MPa,显微硬度大于290HV500,电阻率小于1.0×10-1Ω·cm。
实例3:LiNi0.5Co0.2Mn0.3O2粉体1050℃烧结
将制备的LiNi0.5Co0.2Mn0.3O2粉,在100-200MPa压力下压制成型,脱成型剂后,在高温炉内 1200℃下以每分钟3度升温速率常压烧结5小时,随炉冷却。这样制得的烧结LiNi0.5Co0.2Mn0.3O2靶材,密度大于4.54g/cm3,相对密度≥97.1%,抗弯强度大于100MPa,显微硬度大于320HV500,电阻率小于5×10-2Ω·cm。
实例4:LiNi0.5Co0.2Mn0.3O2粉体1100℃烧结
将制备的LiNi0.5Co0.2Mn0.3O2粉,在100-200MPa压力下压制成型,脱成型剂后,在高温炉内1200℃下以每分钟3度升温速率常压烧结5小时,随炉冷却。这样制得的烧结LiNi0.5Co0.2Mn0.3O2靶材,密度大于4.43g/cm3,相对密度≥96.3%,抗弯强度大于90MPa,显微硬度大于330HV500。电阻率小于8×10-2Ω·cm。
Claims (3)
1.一种高密度LiNi0.5Co0.2Mn0.3O2材料的制备,实验采用球磨(加成型剂)-卸料-干燥-过筛-干压成型-烧结的制备工艺流程,可制备出密度达4.54g/cm3,抗弯强度大于100MPa,显微硬度大于320HV500,电阻率小于5.0×10-2Ω·cm的高性能靶材。
2.对权利要求1所述的LiNi0.5Co0.2Mn0.3O2粉体的烧结,可采用常压烧结工艺,也可将权利要求1所述的LiNi0.5Co0.2Mn0.3O2粉体采用热等静压烧结而得到致密LiNi0.5Co0.2Mn0.3O2材料。
3.利用权利要求1所述LiNi0.5Co0.2Mn0.3O2粉体制备的LiNi0.5Co0.2Mn0.3O2材料,可按照需要制成各种陶瓷制品,主要是溅射镀膜用的靶材,也可用于制造其它多种锂离子电池的电极材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711010524.9A CN109678468A (zh) | 2017-10-18 | 2017-10-18 | 一种三元正极LiNi0.5Co0.2Mn0.3O2材料的制备及烧结方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711010524.9A CN109678468A (zh) | 2017-10-18 | 2017-10-18 | 一种三元正极LiNi0.5Co0.2Mn0.3O2材料的制备及烧结方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109678468A true CN109678468A (zh) | 2019-04-26 |
Family
ID=66183029
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711010524.9A Pending CN109678468A (zh) | 2017-10-18 | 2017-10-18 | 一种三元正极LiNi0.5Co0.2Mn0.3O2材料的制备及烧结方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109678468A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111146402A (zh) * | 2019-12-31 | 2020-05-12 | 无锡晶石新型能源股份有限公司 | 一种凝胶成型工艺烧结制备锂电正极材料的方法 |
CN112599735A (zh) * | 2020-12-11 | 2021-04-02 | 合肥国轩高科动力能源有限公司 | 一种改性ncm622三元正极材料及其制备方法 |
-
2017
- 2017-10-18 CN CN201711010524.9A patent/CN109678468A/zh active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111146402A (zh) * | 2019-12-31 | 2020-05-12 | 无锡晶石新型能源股份有限公司 | 一种凝胶成型工艺烧结制备锂电正极材料的方法 |
CN112599735A (zh) * | 2020-12-11 | 2021-04-02 | 合肥国轩高科动力能源有限公司 | 一种改性ncm622三元正极材料及其制备方法 |
CN112599735B (zh) * | 2020-12-11 | 2022-02-18 | 合肥国轩高科动力能源有限公司 | 一种改性ncm622三元正极材料及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111217347A (zh) | 一种高压实磷酸铁锂材料及其制备方法 | |
CN101752555B (zh) | 一种锂离子电池正极材料磷酸铁锂的制备方法 | |
CN101944591B (zh) | 一种锂离子电池用钛酸锂负极材料及其制备方法 | |
CN106532012B (zh) | 一种硫-生物质碳/过渡金属复合电极材料及其制备方法和应用 | |
CN102820458A (zh) | 一种引入离子液体作为碳源制备含氮碳包覆钛酸锂复合材料的合成方法 | |
CN104659412B (zh) | 含平面三角形基团的锂碳硼氧化物固态电解质材料和电池 | |
CN101955175A (zh) | 一种磷酸亚铁锂的工业制备方法 | |
CN105552369B (zh) | 利用模板法制备三维多孔铌酸钛氧化物的方法及其在锂离子电池中的应用 | |
CN110797529A (zh) | 一种掺杂的高镍高电压ncm正极材料及其制备方法 | |
CN110492097A (zh) | 一种ncm三元复合正极材料及其制备和应用 | |
CN111933942B (zh) | 一种满足高倍率放电循环性能的钠离子电池Na2/3Mn1/2Fe1/4Co1/4O2正极材料的可控调控方法 | |
CN103594708A (zh) | 一种变价铁基复合正极材料及其制备方法 | |
CN114203949A (zh) | 一种层状锰基钠离子电池正极材料及制备方法和应用 | |
CN109786693A (zh) | 一种碳纳米管复合磷酸铁锂正极材料的制备方法 | |
CN107845791B (zh) | 一种双层沥青碳包覆磷酸铁锂正极材料的制备方法 | |
CN105385996A (zh) | 薄膜锂电池用正极材料钴酸锂靶材粉末冶金制备工艺 | |
CN116425212A (zh) | 高熵掺杂层状氧化物及其制备方法、正极材料和钠离子电池 | |
CN103840135B (zh) | 一种钛酸锂材料膜电极的制备方法 | |
CN109678468A (zh) | 一种三元正极LiNi0.5Co0.2Mn0.3O2材料的制备及烧结方法 | |
CN112786860B (zh) | 复合正极材料及其制备方法、正极浆料、正极极片与全固态电池 | |
CN110165286A (zh) | 全固态锂离子电池及其一体化复合烧结制备工艺 | |
CN102157725B (zh) | 微波烧结合成镍钴锰多元锂离子电池正极材料的方法 | |
CN104577111A (zh) | 一种含有含氟磷酸钛化合物的复合材料及其制备方法和用途 | |
CN104085923B (zh) | 过渡金属硫属化物纳米线及其制备方法和储能应用 | |
CN110838579B (zh) | 一种锂硒电池正极材料的制备方法及应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190426 |