WO2022170648A1 - 一种高熵正极材料及其制备方法和应用 - Google Patents

一种高熵正极材料及其制备方法和应用 Download PDF

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WO2022170648A1
WO2022170648A1 PCT/CN2021/078398 CN2021078398W WO2022170648A1 WO 2022170648 A1 WO2022170648 A1 WO 2022170648A1 CN 2021078398 W CN2021078398 W CN 2021078398W WO 2022170648 A1 WO2022170648 A1 WO 2022170648A1
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electrode material
entropy
positive electrode
valent
metal element
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PCT/CN2021/078398
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English (en)
French (fr)
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顾庆文
赛喜·雅勒图
邱报
刘兆平
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中国科学院宁波材料技术与工程研究所
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Priority to AU2021427255A priority Critical patent/AU2021427255A1/en
Priority to KR1020227006453A priority patent/KR20220116422A/ko
Priority to CA3193504A priority patent/CA3193504A1/en
Priority to EP21854796.6A priority patent/EP4293744A1/en
Priority to US17/636,877 priority patent/US20230163290A1/en
Priority to JP2022511376A priority patent/JP7470455B2/ja
Publication of WO2022170648A1 publication Critical patent/WO2022170648A1/zh

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Definitions

  • the invention relates to the technical field of lithium batteries, and more particularly, to a high-entropy positive electrode material and a preparation method and application thereof.
  • Lithium-ion battery is a kind of secondary battery with the characteristics of green environmental protection, high energy density and long cycle life.
  • the requirements for performance indicators of lithium-ion batteries in all aspects are getting higher and higher, especially energy density and safety performance.
  • high energy density lithium-ion batteries often require high specific energy positive and negative electrode materials.
  • lithium ion battery positive electrode materials such as high nickel materials and lithium-rich manganese-based positive electrode materials are High specific capacity is widely valued, but these materials often bring problems of safety, gas production during cycling, and poor cycling stability.
  • the purpose of the present invention is to provide a high-entropy positive electrode material and a preparation method and application thereof.
  • the high-entropy positive electrode material provided by the present invention has a high discharge specific capacity and has a structure in the cycle process. Stable, no oxygen evolution.
  • the present invention provides a high-entropy positive electrode material, which has the general formula shown in formula (I):
  • A is a +2-valent metal element
  • B is a +3-valent metal element
  • C is a +4-valent metal element
  • D is a +5-valent metal element
  • M is a +7-valent element
  • N is a +8-valent metal element element
  • the +2-valent metal element includes one or more of Ni, Be, Mg, Ca, Sr and Ba; the +3-valent metal element includes one or more of Co and Al; The +4-valent metal element includes one or more of Mn, Al, Ti and Zr; the +5-valent metal element includes one or more of Nb, V and T; the +7-valent element includes One or more of F and Cl.
  • the +8 valent element is lattice oxygen.
  • the oxygen element contained in the high-entropy positive electrode material has both +6-valent oxygen and +8-valent oxygen.
  • the present invention also provides a preparation method of the high-entropy positive electrode material described in the above technical solution, comprising the following steps:
  • step b) Mixing the precursor obtained in step a) with lithium, adding oxides containing one or more of A, B, C, D, M, and sintering to obtain Li 1+a A x By C z D b O 2 M c N d cathode material intermediate for high-entropy lithium battery;
  • the reaction temperature of the co-precipitation in step a) is 50°C-70°C
  • the pH is 11-12
  • the reaction time is 15h-60h.
  • the sintering temperature in step b) is 700°C to 900°C, and the time is 10h to 20h.
  • described step a) also comprises:
  • the coprecipitation-synthesized suspension is washed with warm water at 40°C to 60°C, and dried at 90°C to 130°C for 8h to 14h to obtain the precursor.
  • the present invention also provides a high specific energy lithium battery, comprising:
  • Positive electrode material negative electrode material and electrolyte; the positive electrode material is the high-entropy positive electrode material described in the above technical solution.
  • the negative electrode material includes one or more of graphite, silicon carbon material, tin carbon material, red phosphorus, lithium titanate, white phosphorus, lithium metal negative electrode and lithium carbon negative electrode material.
  • the invention provides a high-entropy positive electrode material and a preparation method and application thereof; the high-entropy positive electrode material has the general formula shown in the following formula: Li 1+a A x By C z D b O 2 M c N d ;
  • A is a +2-valent metal element
  • B is a +3-valent metal element
  • C is a +4-valent metal element
  • D is a +5-valent metal element
  • M is a +7-valent element
  • N is a +8-valent element
  • the present invention designs the above-mentioned high-entropy positive electrode material based on the structure of the material itself. Compared with the traditional positive electrode material, it has a high discharge specific capacity and has a stable structure during the cycle process without oxygen evolution, so that the high-capacity positive electrode material can be applied to a high-density positive electrode material.
  • the long-cycle lithium battery system becomes possible, which fundamentally solves the problem of structural stability (gas production) during the charge-discharge cycle of high-capacity cathode materials.
  • the preparation method provided by the present invention has simple process and easy controllable conditions, can obtain stable products, and has broad application prospects.
  • FIG. 1 is a first-round charge-discharge data diagram of a half-cell according to Embodiment 1 of the present invention.
  • the present invention provides a high-entropy positive electrode material, which has the general formula shown in formula (I):
  • A is a +2-valent metal element
  • B is a +3-valent metal element
  • C is a +4-valent metal element
  • D is a +5-valent metal element
  • M is a +7-valent element
  • N is a +8-valent metal element element
  • the high-entropy positive electrode material is a positive electrode material with high-entropy characteristics, and is specifically designed to take into account high capacity, long cycle, and high safety performance (mainly reflected in the absence of safety issues such as spontaneous combustion during battery cycling).
  • Lithium battery cathode material Lithium battery cathode material.
  • the high-capacity cathode materials in the prior art have the problem of poor structural stability during the charge-discharge cycle.
  • the discharge gram capacity of lithium-rich manganese-based cathode materials is as high as 300mAh/g, but there will be structural changes during the cycle process.
  • the performance is poor; in order to solve the problem of poor cycle stability of the high specific energy battery system, especially the gas production problem of the whole battery, many research attempts have been carried out at home and abroad in recent years, and surface and interface treatment methods such as doping and surface coating have been carried out on the positive electrode material.
  • most of the work only delays the oxygen release time of the material, and cannot fundamentally solve the problem of gas production during the material cycle.
  • the present invention designs a high-entropy cathode material from the structure of the material itself. Compared with traditional cathode materials, it has higher discharge specific capacity and has a stable structure without oxygen precipitation during the cycle, so that high-capacity cathode materials can be used in high-capacity cathode materials. The specific energy long-cycle lithium battery system becomes possible.
  • the high-entropy cathode material has the general formula shown in the following formula: Li 1+a A x By C z D b O 2 M c N d ; wherein, A is a +2-valent metal element, and B is +3-valent metal element, C is +4-valent metal element, D is +5-valent metal element, M is +7-valent element, N is +8-valent element; 0 ⁇ a ⁇ 1, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1,0 ⁇ z ⁇ 1,0 ⁇ b ⁇ 1,0 ⁇ c ⁇ 1,d>0.
  • the high-entropy cathode material includes +1 valence lithium, and +2 valence, +3 valence, +4 valence, +5 valence, +6 valence (ie -2 valence) oxygen, +7 valence (ie - 1 price), +8 price (ie 0 price) all elements.
  • the +2-valent metal element preferably includes one or more of Ni, Be, Mg, Ca, Sr and Ba; the +3-valent metal element preferably includes one or more of Co and Al.
  • the +4-valent metal element preferably includes one or more of Mn, Al, Ti and Zr; the +5-valent metal element preferably includes one or more of Nb, V and T; the The +7-valent (ie -1-valent) element preferably includes one or more of F and Cl.
  • the +8-valent (ie, 0-valent) element is lattice oxygen; it can be seen that the oxygen element contained in the high-entropy positive electrode material has both +6-valent (ie -2-valent) oxygen and + 8-valent (ie, 0-valent) oxygen.
  • the high-entropy positive electrode material has the following characteristics during the charging process of the battery: while the above-mentioned metal elements are sequentially activated, the lattice oxygen in the material is also activated, so that the anions and cations are completely activated to have a high discharge rate.
  • the above-mentioned elements of different valences form constraints with each other, which makes the material have a more stable structure, making the material take into account the characteristics of high capacity, high safety, long cycle, etc.; and the 0-valence neutral oxygen also appears as a material At high voltages above 4.45V, the material exerts the electrochemical activity of lattice oxygen, thereby exhibiting high capacity.
  • the present invention also provides a preparation method of the high-entropy positive electrode material described in the above technical solution, comprising the following steps:
  • step b) Mixing the precursor obtained in step a) with lithium, adding oxides containing one or more of A, B, C, D, M, and sintering to obtain Li 1+a A x By C z D b O 2 M c N d cathode material intermediate for high-entropy lithium battery;
  • a precursor containing one or more of A, B, C, D, and M is first synthesized by co-precipitation.
  • the present invention does not have a special limitation on the coprecipitation process, and the technical scheme of performing coprecipitation reaction in a reactor well known to those skilled in the art can be adopted.
  • the reaction temperature of the coprecipitation is preferably 50°C to 70°C, more preferably 55°C to 65°C;
  • the pH of the coprecipitation is preferably 11 to 12, more preferably 11.3 to 11.45;
  • the reaction time of the coprecipitation is preferably 15h-60h, more preferably 20h-55h.
  • the precursor containing one or more of A, B, C, D, and M is Ni 0.08 Co 0.08 Al 0.08 Ti 0.08 Mn 0.6 (OH) 2 precursor; in another preferred embodiment of the present invention, the precursor containing one or more of A, B, C, D, and M is a Ni 0.1 Co 0.1 Mn 0.4 (OH) 2 precursor; In a preferred embodiment, the precursors containing one or more of A, B, C, D, and M are Ni 0.1 Co 0.1 Mn 0.4 (OH) 2 precursors; respectively, according to the above-mentioned general chemical formula in molar ratio It is sufficient to select each raw material or configure each raw material solution to carry out the above-mentioned co-precipitation, which is not particularly limited in the present invention.
  • step a) preferably also comprises:
  • the coprecipitation-synthesized suspension is washed with warm water at 45°C to 50°C, and dried at 100°C to 120°C for 10h to 12h to obtain a precursor.
  • the present invention mixes the obtained precursor with lithium, and simultaneously adds oxides containing one or more of A, B, C, D, M, and mixes them, and then sinters to obtain Li 1+a A x B y C z D b O 2 M c N d is a cathode material intermediate for high-entropy lithium batteries.
  • the lithium and the simultaneously added oxides containing one or more of A, B, C, D, and M select each raw material or configure each raw material in a molar ratio according to the general chemical formula of the above-mentioned intermediate
  • the solution may be mixed, which is not particularly limited in the present invention.
  • the sintering temperature is preferably 700°C to 900°C, more preferably 780°C to 835°C; the sintering time is preferably 10h to 20h, more preferably 15h to 18h.
  • the present invention After obtaining the Li 1+a A x By C z D b O 2 M c N d high- entropy lithium battery cathode material intermediate, the present invention will obtain the Li 1+a A x By C z D b O 2
  • the high-entropy cathode material intermediate of McNd high- entropy lithium battery is surface-treated and coated to obtain a high-entropy cathode material.
  • the present invention has no special limitation on the process of the surface treatment, and the technical solution of surface acid treatment and washing off the residual alkali on the surface of the material well known to those skilled in the art can be used.
  • the coating preferably adopts surface alumina coating known to those skilled in the art.
  • the preparation method provided by the invention has simple process, easy controllable conditions, can obtain stable products, and has broad application prospects.
  • the present invention also provides a high specific energy lithium battery, comprising:
  • Positive electrode material negative electrode material and electrolyte; the positive electrode material is the high-entropy positive electrode material described in the above technical solution.
  • the negative electrode material preferably includes one of graphite (including natural graphite and artificial graphite), silicon carbon material, tin carbon material, red phosphorus, lithium titanate, white phosphorus, lithium metal negative electrode and lithium carbon negative electrode material or more, more preferably silicon carbon material, lithium metal negative electrode or lithium carbon negative electrode material; thereby forming a high specific energy power battery with the above-mentioned high entropy positive electrode material.
  • the electrolyte includes one or more of a liquid electrolyte, a gel electrolyte and a solid electrolyte; the present invention has no particular limitation on its source.
  • the high specific energy lithium battery preferably further includes a separator; the present invention does not have a special limitation on the separator, and a separator known to those skilled in the art for preparing lithium batteries can be used.
  • the high specific energy lithium battery is a lithium ion battery; the present invention combines the above-mentioned high entropy positive electrode material with the negative electrode material of conventional lithium ion battery (such as graphite, silicon carbon composite negative electrode material, tin carbon composite negative electrode material, one or more of red phosphorus, lithium titanate, white phosphorus and other negative electrode materials), diaphragm, electrolyte, etc. are assembled into a lithium ion battery, so as to realize the high entropy positive electrode material provided by the present invention in the lithium ion battery. application.
  • conventional lithium ion battery such as graphite, silicon carbon composite negative electrode material, tin carbon composite negative electrode material, one or more of red phosphorus, lithium titanate, white phosphorus and other negative electrode materials
  • the high specific energy lithium battery is a lithium metal battery; the present invention combines the above-mentioned high-entropy positive electrode material with a lithium metal negative electrode (such as one of lithium sheets, lithium strips, and lithium foils or A high-energy density lithium metal battery is assembled into a high-energy density lithium metal battery, and the application of the high-entropy positive electrode material provided by the present invention in a lithium metal battery is realized.
  • a lithium metal negative electrode such as one of lithium sheets, lithium strips, and lithium foils or
  • the high-specific-energy lithium battery is a solid-state lithium-ion battery; the present invention combines the above-mentioned high-entropy positive electrode material with a conventional lithium-ion battery negative electrode material (such as graphite, silicon-carbon composite negative electrode material, tin One or more of carbon composite negative electrode materials, red phosphorus, lithium titanate, white phosphorus and other negative electrode materials), solid electrolytes, etc. are assembled into solid-state lithium-ion batteries, so that the high-entropy positive electrode materials provided by the present invention can be used in solid-state lithium-ion batteries.
  • a conventional lithium-ion battery negative electrode material such as graphite, silicon-carbon composite negative electrode material, tin
  • carbon composite negative electrode materials, red phosphorus, lithium titanate, white phosphorus and other negative electrode materials such as graphite, silicon-carbon composite negative electrode material, tin
  • solid electrolytes, etc. are assembled into solid-state lithium-ion batteries, so that the high-entropy positive electrode materials provided by
  • the high-specific energy lithium battery is a solid-state lithium metal battery; the present invention combines the above-mentioned high-entropy positive electrode material with a lithium metal negative electrode (such as one of a lithium sheet, a lithium strip, and a lithium foil). (or more), solid electrolyte, etc., are assembled into a high-energy density lithium metal battery, so as to realize the application of the high-entropy positive electrode material provided by the present invention in a solid-state lithium metal battery.
  • a lithium metal negative electrode such as one of a lithium sheet, a lithium strip, and a lithium foil
  • the invention provides a high-entropy positive electrode material and a preparation method and application thereof; the high-entropy positive electrode material has the general formula shown in the following formula: Li 1+a A x By C z D b O 2 M c N d ;
  • A is a +2-valent metal element
  • B is a +3-valent metal element
  • C is a +4-valent metal element
  • D is a +5-valent metal element
  • M is a +7-valent element
  • N is a +8-valent element
  • the present invention designs the above-mentioned high-entropy positive electrode material based on the structure of the material itself. Compared with the traditional positive electrode material, it has a high discharge specific capacity and has a stable structure during the cycle process without oxygen evolution, so that the high-capacity positive electrode material can be applied to a high-density positive electrode material.
  • the long-cycle lithium battery system becomes possible, which fundamentally solves the problem of structural stability (gas production) during the charge-discharge cycle of high-capacity cathode materials.
  • the preparation method provided by the present invention has simple process and easy controllable conditions, can obtain stable products, and has broad application prospects.
  • Ni 0.08 Co 0.08 Al 0.08 Ti 0.08 Mn 0.6 (OH) 2 precursor was synthesized by co-precipitation method, and NiSO 4 with a molar concentration of 2 mol/L was prepared in a molar ratio of 8:8:8:60.
  • Ni 0.08 Co is obtained after the reaction for 20 hours.
  • the suspension of 0.08 Al 0.08 Ti 0.08 Mn 0.6 (OH) 2 ; the suspension of Ni 0.08 Co 0.08 Al 0.08 Ti 0.08 Mn 0.6 (OH) 2 was washed with warm water at 45°C and dried at 100°C for 10 hours to obtain Form Ni 0.08 Co 0.08 Al 0.08 Ti 0.08 Mn 0.6 (OH) 2 precursor;
  • Ni shows a valence of +2 in the material system
  • Co shows a valence of +3 in the material system
  • Al shows a valence of +3 in the material system
  • Ti shows a valence of +4 in the material system
  • Mn shows a valence of +4 in the material system.
  • Nb shows a valence of +5 in the material system
  • F shows a valence of -1 in the material system
  • O shows an electrically neutral oxygen with a valence of -2 and 0 in the material system.
  • the first-time efficiency of the material half-cell reaches 93%, and the discharge gram capacity reaches 310mAh/g.
  • the electrochemical data is shown in Figure 1; the full-cell negative graphite has a capacity retention rate of 92% for 1000 cycles in the voltage range of 2.8-4.55V. It is suitable for the basic needs of high specific energy power battery applications.
  • Ni 0.1 Co 0.1 Mn 0.4 (OH) 2 precursor was synthesized by the co-precipitation method, and a mixed solution of NiSO 4 , CoSO 4 , and MnSO 4 with a molar concentration of 2 mol/L was prepared in a molar ratio of 1:1:4 , configure the ammonia solution with a molar concentration of 1.2mol/L, configure a sodium hydroxide solution with a molar concentration of 4mol/L, and add the prepared mixed solution, ammonia solution, and sodium hydroxide solution according to the volume ratio of 2:2:1.5.
  • a co-precipitation reaction was carried out.
  • Ni 0.1 Co 0.1 Mn 0.4 (OH) 2 was obtained; Ni 0.1 Co 0.1
  • the suspension of Mn 0.4 (OH) 2 was washed, washed with warm water at 50 ° C, and dried at 120 ° C for 12 hours to obtain a Ni 0.1 Co 0.1 Mn 0.4 (OH) 2 precursor;
  • Ni shows a valence of +2 in the material system
  • Co shows a valence of +3 in the material system
  • Al shows a valence of +3 in the material system
  • Ti shows a valence of +4 in the material system
  • Mn shows a valence of +4 in the material system.
  • Nb shows a valence of +5 in the material system
  • F shows a valence of -1 in the material system
  • O shows an electrically neutral oxygen with a valence of -2 and 0 in the material system.
  • the first-time efficiency of the material half-cell reaches 94%
  • the discharge gram capacity reaches 280mAh/g
  • the capacity retention rate of the full-cell anode graphite for 1000 cycles in the voltage range of 2.8-4.65V is 94%. It is suitable for the basic needs of high specific energy power battery applications.
  • Ni 0.1 Co 0.1 Mn 0.4 (OH) 2 precursor was synthesized by the co-precipitation method, and a mixed solution of NiSO 4 , CoSO 4 , and MnSO 4 with a molar concentration of 2 mol/L was prepared in a molar ratio of 1:1:4 , configure the ammonia solution with a molar concentration of 1.2mol/L, configure a sodium hydroxide solution with a molar concentration of 4mol/L, and add the prepared mixed solution, ammonia solution, and sodium hydroxide solution according to the volume ratio of 2:2:1.5.
  • a co-precipitation reaction was carried out.
  • the temperature of the reaction kettle was controlled at 62°C, and the pH of the system was controlled at about 11.45.
  • a suspension of Ni 0.1 Co 0.1 Mn 0.4 (OH) 2 was obtained;
  • the suspension of Mn 0.4 (OH) 2 was washed with warm water at 45° C., and dried at 110° C. for 10 hours to obtain a Ni 0.1 Co 0.1 Mn 0.4 (OH) 2 precursor;
  • Li 1.2 Ni 0.1 Mg 0.05 Co 0.1 Al 0.1 Zr 0.1 Mn0.35Nb0.1O 2+ ⁇ F 0.1 high-entropy lithium battery positive electrode material is subjected to surface acid treatment, and the residual alkali on the surface of the material is washed away.
  • the stable high-entropy lithium battery positive electrode material Li 1.2 Ni 0.1 Mg 0.05 Co 0.1 Al 0.1 Zr 0.1 Mn0.35Nb0.1O 2+ ⁇ F 0.1 is obtained by coating.
  • Ni shows +2 valence in the material system
  • Mg shows +2 valence in the material system
  • Co shows +3 valence in the material system
  • Al shows +3 valence in the material system
  • Zr shows in the material system. It shows +4 valence
  • Mn shows +4 valence in the material system
  • Nb shows +5 valence in the material system
  • F shows -1 valence in the material system
  • O shows -2 valence and 0 electric neutrality in the material system of oxygen.
  • the first efficiency of the material half-cell reaches 94%
  • the discharge gram capacity reaches 280mAh/g
  • the energy density of the full-cell metal lithium anode reaches 500Wh/Kg
  • the capacity retention rate for 1000 cycles in the voltage range of 2.8-4.65V is 95%. It is suitable for the basic needs of high specific energy power battery applications.

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Abstract

提供了一种高熵正极材料及其制备方法和应用；高熵正极材料具有下式所示通式：Li 1+aA xB yC zD bO 2M cN d；其中，A为+2价金属元素，B为+3价金属元素，C为+4价金属元素，D为+5价金属元素，M为+7价元素，N为+8价元素；0≤a＜1，0＜x＜1，0＜y＜1，0＜z＜1，0＜b＜1，0＜c＜1，d＞0。从材料本身结构出发设计出的高熵正极材料，与传统正极材料相比，具有高的放电比容量，同时在循环过程中结构稳定，无氧气析出，从而使得高容量正极材料应用于高比能长循环锂电池体系成为可能，从根本上解决高容量正极材料充放电循环过程中结构稳定性和产气的问题。

Description

一种高熵正极材料及其制备方法和应用
本申请要求于2021年2月10日提交中国专利局、申请号为202110183314.X、发明名称为“一种高熵正极材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及锂电池技术领域，更具体地说，是涉及一种高熵正极材料及其制备方法和应用。
背景技术
近年来，随着智能手机、平板电脑、电子手环等各类消费类电子产品日新月异、节能环保的电动交通工具市场飞速增长以及储能电池市场崭露头角，作为这些产品电源的锂离子电池的市场得以飞速发展。锂离子电池是一种具有绿色环保、能量密度高和循环寿命长等特点的二次电池。随着人们对锂离子电池使用范围的扩大和依赖程度的递增，对锂离子电池各方面的性能指标的要求也越来越高，特别是能量密度和安全性能。就能量密度而言，高能量密度锂离子电池往往需要高比能正负极材料，现有高比能正极材料体系中，锂离子电池正极材料如高镍材料、富锂锰基正极材料因其高的比容量受到大家广泛重视，但是这些材料往往带来安全性、循环过程中产气以及循环稳定性差的问题。
为解决实现高比能电池体系循环稳定性差的问题，尤其是全电池产气问题，近年来国内外开展很多研究尝试，对正极材料进行掺杂、表面包覆等表界面处理手段。但是，多数工作仅仅是延缓材料氧气释放时间，并不能从根本上解决材料循环过程中产气问题。
发明内容
有鉴于此，本发明的目的在于提供一种高熵正极材料及其制备方法和应用，本发明提供的高熵正极材料与传统正极材料相比，具有高的放电比容量同时在循环过程中结构稳定，无氧气析出。
本发明提供了一种高熵正极材料，具有式(I)所示通式：
Li 1+aA xB yC zD bO 2M cN d     式(I)；
式(I)中，A为+2价金属元素，B为+3价金属元素，C为+4价金属元素，D为+5价金属元素，M为+7价元素，N为+8价元素；
0≤a＜1，0＜x＜1，0＜y＜1，0＜z＜1，0＜b＜1，0＜c＜1，d＞0。
优选的，所述+2价金属元素包括Ni、Be、Mg、Ca、Sr和Ba中的一种或多种；所述+3价金属元素包括Co和Al中的一种或多种；所述+4价金属元素包括Mn、Al、Ti和Zr中的一种或多种；所述+5价金属元素包括Nb、V和T中的一种或多种；所述+7价元素包括F和Cl中的一种或多种。
优选的，所述+8价元素为晶格氧。
优选的，所述高熵正极材料中含有的氧元素同时具有+6价氧和+8价氧。
本发明还提供了一种上述技术方案所述的高熵正极材料的制备方法，包括以下步骤：
a)通过共沉淀合成含有A、B、C、D、M的一种或多种的前驱体；
b)将步骤a)得到的前驱体混锂，同时加入含有A、B、C、D、M的一种或多种的氧化物混合后烧结，得到Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体；
c)将步骤b)得到的Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体经过表面处理、包覆，得到高熵正极材料。
优选的，步骤a)中所述共沉淀的反应温度为50℃～70℃，pH为11～12，反应时间为15h～60h。
优选的，步骤b)中所述烧结的温度为700℃～900℃，时间为10h～20h。
优选的，所述步骤a)还包括：
将共沉淀合成的悬浊液用40℃～60℃温水洗涤，经90℃～130℃烘干8h～14h后得到前躯体。
本发明还提供了一种高比能锂电池，包括：
正极材料、负极材料和电解质；所述正极材料为上述技术方案所述的高熵正极材料。
优选的，所述负极材料包括石墨、硅碳材料、锡碳材料、红磷、钛酸锂、白磷、锂金属负极和锂碳负极材料中的一种或多种。
本发明提供了一种高熵正极材料及其制备方法和应用；所述高熵正极材料具有下式所示通式：Li 1+aA xB yC zD bO 2M cN d；其中，A为+2价金属元素，B为+3价金属元素，C为+4价金属元素，D为+5价金属元素，M为+7价元素，N为+8价元素；0≤a＜1，0＜x＜1，0＜y＜1，0＜z＜1，0＜b＜1，0＜c＜1，d＞0。本发明从材料本身结构出发设计出上述高熵正极材料，与传统正极材料相比，具有高的放电比容量同时在循环过程中结构稳定，无氧气析出，从而使得高容量正极材料应用于高比能长循环锂电池体系成为可能，从根本上解决高容量正极材料充放电循环过程中结构稳定性(产气)问题。
另外，本发明提供的制备方法工艺简单、条件易控，能够获得稳定的产品，具有广阔的应用前景。
附图说明
图1为本发明实施例1的半电池首圈充放电数据图。
具体实施方式
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种高熵正极材料，具有式(I)所示通式：
Li 1+aA xB yC zD bO 2M cN d   式(I)；
式(I)中，A为+2价金属元素，B为+3价金属元素，C为+4价金属元素，D为+5价金属元素，M为+7价元素，N为+8价元素；
0≤a＜1，0＜x＜1，0＜y＜1，0＜z＜1，0＜b＜1，0＜c＜1，d＞0。
在本发明中，所述高熵正极材料是一种具有高熵特性的正极材料，具体为兼顾高容量、长循环、高安全性能(主要体现在电池循环过程中不发生自燃等安全问题)的锂电池正极材料。目前，现有技术中的高容量正极材料存在充放电循环过程中结构稳定性差的问题，如富锂锰基正极材料其放电克容量高达300mAh/g，但是其在循环过程中会存在结构改变，从而性能差；为解决实现 高比能电池体系循环稳定性差的问题，尤其是全电池产气问题，近年来国内外开展很多研究尝试，对正极材料进行掺杂、表面包覆等表界面处理手段；但是，多数工作仅仅是延缓材料氧气释放时间，并不能从根本上解决材料循环过程中产气问题。基于此本发明从材料本身结构出发设计出一款高熵正极材料，与传统正极材料相比具有高的放电比容量同时在循环过程中结构稳定无氧气析出，从而使得高容量正极材料应用于高比能长循环锂电池体系成为可能。
在本发明中，所述高熵正极材料具有下式所示通式：Li 1+aA xB yC zD bO 2M cN d；其中，A为+2价金属元素，B为+3价金属元素，C为+4价金属元素，D为+5价金属元素，M为+7价元素，N为+8价元素；0≤a＜1，0＜x＜1，0＜y＜1，0＜z＜1，0＜b＜1，0＜c＜1，d＞0。由此可知，所述高熵正极材料包括+1价锂、以及+2价、+3价、+4价、+5价、+6价(即-2价)氧、+7价(即-1价)、+8价(即0价)所有元素。
在本发明中，所述+2价金属元素优选包括Ni、Be、Mg、Ca、Sr和Ba中的一种或多种；所述+3价金属元素优选包括Co和Al中的一种或多种；所述+4价金属元素优选包括Mn、Al、Ti和Zr中的一种或多种；所述+5价金属元素优选包括Nb、V和T中的一种或多种；所述+7价(即-1价)元素优选包括F和Cl中的一种或多种。
在本发明中，所述+8价(即0价)元素为晶格氧；由此可知，所述高熵正极材料中含有的氧元素同时具有+6价(即-2价)氧和+8价(即0价)氧。在本发明中，所述高熵正极材料在电池充电过程中存在以下特点：上述金属元素依次被激活的同时，材料中晶格氧也被激活，从而阴阳离子完全被激活使其具有高的放电比容量；同时上述不同价态的元素彼此之间形成约束，使得材料具有更加稳定结构，使得材料兼顾高容量、高安全、长循环等特征；并且，0价电中性的氧还表现为材料在高电压下4.45V以上材料发挥了晶格氧的电化学活性，从而表现为高容量。
本发明还提供了一种上述技术方案所述的高熵正极材料的制备方法，包括以下步骤：
a)通过共沉淀合成含有A、B、C、D、M的一种或多种的前驱体；
b)将步骤a)得到的前驱体混锂，同时加入含有A、B、C、D、M的一种 或多种的氧化物混合后烧结，得到Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体；
c)将步骤b)得到的Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体经过表面处理、包覆，得到高熵正极材料。
本发明首先通过共沉淀合成含有A、B、C、D、M的一种或多种的前驱体。本发明对所述共沉淀的过程没有特殊限制，采用本领域技术人员熟知的在反应釜中进行共沉淀反应的技术方案即可。在本发明中，所述共沉淀的反应温度优选为50℃～70℃，更优选为55℃～65℃；所述共沉淀的pH优选为11～12，更优选为11.3～11.45；所述共沉淀的反应时间优选为15h～60h，更优选为20h～55h。
在本发明一个优选的实施例中，所述含有A、B、C、D、M的一种或多种的前驱体为Ni 0.08Co 0.08Al 0.08Ti 0.08Mn 0.6(OH) 2前驱体；在本发明另一个优选的实施例中，所述含有A、B、C、D、M的一种或多种的前驱体为Ni 0.1Co 0.1Mn 0.4(OH) 2前驱体；在本发明另一个优选的实施例中，所述含有A、B、C、D、M的一种或多种的前驱体为Ni 0.1Co 0.1Mn 0.4(OH) 2前驱体；分别按照上述化学通式按摩尔比例选择各原料或配置各原料溶液进行上述共沉淀即可，本发明对此没有特殊限制。
在本发明中，所述步骤a)优选还包括：
将共沉淀合成的悬浊液用40℃～60℃温水洗涤，经90℃～130℃烘干8h～14h后得到前躯体；
更优选为：
将共沉淀合成的悬浊液用45℃～50℃温水洗涤，经100℃～120℃烘干10h～12h后得到前躯体。
得到所述前驱体后，本发明将得到的前驱体混锂，同时加入含有A、B、C、D、M的一种或多种的氧化物混合后烧结，得到Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体。在本发明中，所述锂及同时加入的含有A、B、C、D、M的一种或多种的氧化物，按照上述中间体的化学通式按摩尔比例选择各原料或配置各原料溶液进行混合即可，本发明对此没有特殊限制。
在本发明中，所述烧结的温度优选为700℃～900℃，更优选为780℃～835℃；所述烧结的时间优选为10h～20h，更优选为15h～18h。
得到所述Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体后，本发明将得到的Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体经过表面处理、包覆，得到高熵正极材料。本发明对所述表面处理的过程没有特殊限制，采用本领域技术人员熟知的表面酸处理、洗去材料表面的残留碱的技术方案即可。
在本发明中，所述包覆优选采用本领域技术人员熟知的表面氧化铝包覆即可。
本发明提供的制备方法工艺简单、条件易控，能够获得稳定的产品，具有广阔的应用前景。
本发明还提供了一种高比能锂电池，包括：
正极材料、负极材料和电解质；所述正极材料为上述技术方案所述的高熵正极材料。
在本发明中，所述负极材料优选包括石墨(包括天然石墨和人造石墨)、硅碳材料、锡碳材料、红磷、钛酸锂、白磷、锂金属负极和锂碳负极材料中的一种或多种，更优选为硅碳材料、锂金属负极或锂碳负极材料；从而与上述高熵正极材料组成高比能动力电池。
在本发明中，所述电解质包括液态电解液、凝胶态电解质和固体电解质中的一种或多种；本发明对其来源没有特殊限制。
在本发明中，所述高比能锂电池优选还包括隔膜；本发明对所述隔膜没有特殊限制，采用本领域技术人员熟知的用于制备锂电池的隔膜即可。
在本发明一个优选的实施例中，所述高比能锂电池为锂离子电池；本发明将上述高熵正极材料与常规锂离子电池的负极材料(如石墨、硅碳复合负极材料、锡碳复合负极材料、红磷、钛酸锂、白磷等负极材料中的一种或者多种)、隔膜、电解液等组装成锂离子电池，实现本发明提供的高熵正极材料在锂离子电池中的应用。
在本发明另一个优选的实施例中，所述高比能锂电池为锂金属电池；本发明将上述高熵正极材料与锂金属负极(如锂片、锂带、锂箔中的一种或多种)、隔膜、电解液等组装成高能量密度锂金属电池，实现本发明提供的高熵正极材料在锂金属电池中的应用。
在本发明另一个优选的实施例中，所述高比能锂电池为固态锂离子电池； 本发明将上述高熵正极材料与常规锂离子电池负极材料(如石墨、硅碳复合负极材料、锡碳复合负极材料、红磷、钛酸锂、白磷等负极材料中的一种或者多种)、固体电解质等组装成固态锂离子电池，实现本发明提供的高熵正极材料在固态锂离子电池中的应用。
在本发明另一个优选的实施例中，所述高比能锂电池为固态锂金属电池；本发明将上述高熵正极材料与锂金属负极(如锂片、锂带、锂箔中的一种或多种)、固体电解质等组装成高能量密度锂金属电池，实现本发明提供的高熵正极材料在固态锂金属电池中的应用。
本发明提供了一种高熵正极材料及其制备方法和应用；所述高熵正极材料具有下式所示通式：Li 1+aA xB yC zD bO 2M cN d；其中，A为+2价金属元素，B为+3价金属元素，C为+4价金属元素，D为+5价金属元素，M为+7价元素，N为+8价元素；0≤a＜1，0＜x＜1，0＜y＜1，0＜z＜1，0＜b＜1，0＜c＜1，d＞0。本发明从材料本身结构出发设计出上述高熵正极材料，与传统正极材料相比，具有高的放电比容量同时在循环过程中结构稳定，无氧气析出，从而使得高容量正极材料应用于高比能长循环锂电池体系成为可能，从根本上解决高容量正极材料充放电循环过程中结构稳定性(产气)问题。
另外，本发明提供的制备方法工艺简单、条件易控，能够获得稳定的产品，具有广阔的应用前景。
为了进一步说明本发明，下面通过以下实施例进行详细说明。以下实施例中所用的试剂均为市售。
实施例1
(1)采用共沉淀法合成Ni 0.08Co 0.08Al 0.08Ti 0.08Mn 0.6(OH) 2前驱体，按摩尔比8：8：8：8：60的比例配置摩尔浓度为2mol/L的NiSO 4、CoSO 4、NaAlO 2、钛酸四丁酯、MnSO 4的混合溶液、配置摩尔浓度为1.2mol/L的氨水溶液、配置摩尔浓度为5mol/L的氢氧化钠溶液，按照体积比2：0.5：1将配好的混合溶液、氨水溶液、氢氧化钠溶液分别加入反应釜中，进行共沉淀反应，反应过程中控制反应釜温度55℃，控制体系pH在11.3左右，反应20h后得到Ni 0.08Co 0.08Al 0.08Ti 0.08Mn 0.6(OH) 2的悬浊液；将Ni 0.08Co 0.08Al 0.08Ti 0.08Mn 0.6(OH) 2的悬浊液用45℃温水洗涤，经100℃烘干10小时后得到形 Ni 0.08Co 0.08Al 0.08Ti 0.08Mn 0.6(OH) 2前躯体；
(2)将上述材料前驱体与碳酸锂、LiF、五氧化二铌按照Li 1.2Ni 0.08Co 0.08Al 0.08Ti 0.08Mn 0.6Nb 0.08O 2+δF 0.08比例混合经780℃、16h烧结得到高熵正极材料；
(3)将上述Li 1.2Ni 0.08Co 0.08Al 0.08Ti 0.08Mn 0.6Nb 0.08O 2+δF 0.08高熵锂电池正极材料经过表面酸处理、洗去材料表面的残留碱在进行表面氧化铝包覆得到稳定的高熵锂电池正极材料Li 1.2Ni 0.08Co 0.08Al 0.08Ti 0.08Mn 0.6Nb 0.08O 2+δF 0.08。
(4)将上述高熵锂电池正极材料与负极材料石墨、隔膜、电解液等组装成锂离子电池。
上述材料经过XPS测试Ni在材料体系中显示+2价，Co在材料体系中显示+3价，Al在材料体系中显示+3价，Ti在材料体系中显示+4价，Mn在材料体系中显示+4价，Nb在材料体系中显示+5价，F在材料体系中显示-1价，O在材料体系中显示-2价和0价电中性的氧。材料半电池的首次效率达到93％，放电克容量达到310mAh/g，电化学数据见图1；全电池负极石墨2.8-4.55V电压范围内循环1000圈容量保持率为92％。适用于高比能动力电池应用基本需求。
实施例2
(1)采用共沉淀法合成Ni 0.1Co 0.1Mn 0.4(OH) 2前驱体，按摩尔比1：1：4的比例配置摩尔浓度为2mol/L的NiSO 4、CoSO 4、MnSO 4的混合溶液、配置摩尔浓度为1.2mol/L的氨水溶液、配置摩尔浓度为4mol/L的氢氧化钠溶液，按照体积比2：2：1.5将配好的混合溶液、氨水溶液、氢氧化钠溶液分别加入反应釜中，进行共沉淀反应，反应过程中控制反应釜温度65℃，控制体系pH在11.45左右，反应28h后得到Ni 0.1Co 0.1Mn 0.4(OH) 2的悬浊液；将Ni 0.1Co 0.1Mn 0.4(OH) 2的悬浊液洗涤，用50℃温水洗涤，经120℃烘干12小时后得到形Ni 0.1Co 0.1Mn 0.4(OH) 2前躯体；
(2)将上述材料前驱体与碳酸锂、纳米氧化铝、纳米二氧化钛、LiF、五氧化二铌按照Li 1.2Ni 0.1Co 0.1Al 0.1Ti 0.1Mn 0.4Nb 0.1O 2+δF 0.1比例混合经815℃、18h烧结得到高熵正极材料；
(3)将上述Li 1.2Ni 0.1Co 0.1Al 0.1Ti 0.1Mn 0.4Nb 0.1O 2+δF 0.1高熵锂电池正极材料经过表面酸处理、洗去材料表面的残留碱在进行表面氧化铝包覆得到稳定的高熵 锂电池正极材料Li 1.2Ni 0.1Co 0.1Al 0.1Ti 0.1Mn 0.4Nb 0.1O 2+δF 0.1。
(4)将上述高熵锂电池正极材料与硅碳-石墨复合负极材料、隔膜、电解液等组装成锂离子电池。
上述材料经过XPS测试Ni在材料体系中显示+2价，Co在材料体系中显示+3价，Al在材料体系中显示+3价，Ti在材料体系中显示+4价，Mn在材料体系中显示+4价，Nb在材料体系中显示+5价，F在材料体系中显示-1价，O在材料体系中显示-2价和0价电中性的氧。材料半电池的首次效率达到94％，放电克容量达到280mAh/g，全电池负极石墨2.8-4.65V电压范围内循环1000圈容量保持率为94％。适用于高比能动力电池应用基本需求。
实施例3
(1)采用共沉淀法合成Ni 0.1Co 0.1Mn 0.4(OH) 2前驱体，按摩尔比1：1：4的比例配置摩尔浓度为2mol/L的NiSO 4、CoSO 4、MnSO 4的混合溶液、配置摩尔浓度为1.2mol/L的氨水溶液、配置摩尔浓度为4mol/L的氢氧化钠溶液，按照体积比2：2：1.5将配好的混合溶液、氨水溶液、氢氧化钠溶液分别加入反应釜中，进行共沉淀反应，反应过程中控制反应釜温度62℃，控制体系pH在11.45左右，反应55h后得到Ni 0.1Co 0.1Mn 0.4(OH) 2的悬浊液；将Ni 0.1Co 0.1Mn 0.4(OH) 2的悬浊液用45℃温水洗涤，经110℃烘干10小时后得到形Ni 0.1Co 0.1Mn 0.4(OH) 2前躯体；
(2)将上述材料前驱体与碳酸锂、纳米二氧化镁、纳米氧化铝、纳米氧化锆、LiF、五氧化二铌按照Li 1.2Ni 0.1Mg 0.05Co 0.1Al 0.1Zr 0.1Mn0.35Nb0.1O 2+δF 0.1比例混合经835℃、15h烧结得到高熵正极材料；
(3)将上述Li 1.2Ni 0.1Mg 0.05Co 0.1Al 0.1Zr 0.1Mn0.35Nb0.1O 2+δF 0.1高熵锂电池正极材料经过表面酸处理、洗去材料表面的残留碱在进行表面氧化铝包覆得到稳定的高熵锂电池正极材料Li 1.2Ni 0.1Mg 0.05Co 0.1Al 0.1Zr 0.1Mn0.35Nb0.1O 2+δF 0.1。
(4)将上述高熵锂电池正极材料与锂金属负极材料、隔膜、电解液等组装成锂金属电池。
上述材料经过XPS测试Ni在材料体系中显示+2价，Mg在材料体系中显示+2价，Co在材料体系中显示+3价，Al在材料体系中显示+3价，Zr在材料体系中显示+4价，Mn在材料体系中显示+4价，Nb在材料体系中显示+5价， F在材料体系中显示-1价，O在材料体系中显示-2价和0价电中性的氧。材料半电池的首次效率达到94％，放电克容量达到280mAh/g，全电池金属锂负极能量密度到达500Wh/Kg，2.8-4.65V电压范围内循环1000圈容量保持率为95％。适用于高比能动力电池应用基本需求。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种高熵正极材料，其特征在于，具有式(I)所示通式：
    Li 1+aA xB yC zD bO 2M cN d  式(I)；
    式(I)中，A为+2价金属元素，B为+3价金属元素，C为+4价金属元素，D为+5价金属元素，M为+7价元素，N为+8价元素；
    0≤a＜1，0＜x＜1，0＜y＜1，0＜z＜1，0＜b＜1，0＜c＜1，d＞0。
  2. 根据权利要求1所述的高熵正极材料，其特征在于，所述+2价金属元素包括Ni、Be、Mg、Ca、Sr和Ba中的一种或多种；所述+3价金属元素包括Co和Al中的一种或多种；所述+4价金属元素包括Mn、Al、Ti和Zr中的一种或多种；所述+5价金属元素包括Nb、V和T中的一种或多种；所述+7价元素包括F和Cl中的一种或多种。
  3. 根据权利要求1所述的高熵正极材料，其特征在于，所述+8价元素为晶格氧。
  4. 根据权利要求3所述的高熵正极材料，其特征在于，所述高熵正极材料中含有的氧元素同时具有+6价氧和+8价氧。
  5. 一种权利要求1～4任一项所述的高熵正极材料的制备方法，其特征在于，包括以下步骤：
    a)通过共沉淀合成含有A、B、C、D、M的一种或多种的前驱体；
    b)将步骤a)得到的前驱体混锂，同时加入含有A、B、C、D、M的一种或多种的氧化物混合后烧结，得到Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体；
    c)将步骤b)得到的Li 1+aA xB yC zD bO 2M cN d高熵锂电池正极材料中间体经过表面处理、包覆，得到高熵正极材料。
  6. 根据权利要求5所述的制备方法，其特征在于，步骤a)中所述共沉淀的反应温度为50℃～70℃，pH为11～12，反应时间为15h～60h。
  7. 根据权利要求5所述的制备方法，其特征在于，步骤b)中所述烧结的温度为700℃～900℃，时间为10h～20h。
  8. 根据权利要求5～7任一项所述的制备方法，其特征在于，所述步骤a) 还包括：
    将共沉淀合成的悬浊液用40℃～60℃温水洗涤，经90℃～130℃烘干8h～14h后得到前躯体。
  9. 一种高比能锂电池，其特征在于，包括：
    正极材料、负极材料和电解质；所述正极材料为权利要求1～4任一项所述的高熵正极材料。
  10. 根据权利要求9所述的高比能锂电池，其特征在于，所述负极材料包括石墨、硅碳材料、锡碳材料、红磷、钛酸锂、白磷、锂金属负极和锂碳负极材料中的一种或多种。
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