WO2020151143A1 - Prelithiation material, preparation method thereof, and lithium battery - Google Patents

Prelithiation material, preparation method thereof, and lithium battery Download PDF

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WO2020151143A1
WO2020151143A1 PCT/CN2019/088253 CN2019088253W WO2020151143A1 WO 2020151143 A1 WO2020151143 A1 WO 2020151143A1 CN 2019088253 W CN2019088253 W CN 2019088253W WO 2020151143 A1 WO2020151143 A1 WO 2020151143A1
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lithiation
sintering
crushing
oxide
metal elements
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PCT/CN2019/088253
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French (fr)
Chinese (zh)
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闫昭
罗飞
李泓
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溧阳天目先导电池材料科技有限公司
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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
    • 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
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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

Definitions

  • the invention relates to the technical field of lithium battery materials, in particular to a pre-lithiation material, a preparation method thereof, and a lithium battery.
  • lithium-ion batteries Because of its high output voltage, high energy density, long cycle life, good safety performance, and no memory effect, lithium-ion batteries have been successfully applied to the field of mobile power supplies as the main energy storage device. In order to further meet the demand for energy storage devices for grid energy storage, electric vehicles and consumer electronics, electrode materials and lithium battery systems with longer cycle life, better safety, and higher energy density have become research hotspots.
  • the negative electrode of commercial lithium-ion batteries mainly uses graphite materials.
  • the theoretical capacity of graphite materials is 372mAh/g, which limits the overall specific capacity of lithium-ion batteries. It has become a trend to gradually replace graphite materials with alloy anode materials with higher theoretical capacity.
  • most high specific capacity anode materials generally have an irreversible reaction with lithium ions in the first week, which consumes the lithium source in the lithium battery and reduces the overall specific capacity of the battery.
  • the pre-lithiation technology proposes to replenish lithium ions in the first week of battery formation, which becomes the most possible solution.
  • most of the existing prelithiation technologies have problems such as difficult control of the prelithiation amount, small prelithiation amount, side reactions, high environmental requirements, and room temperature instability. Therefore, there is an urgent need to propose a prelithiation material and Its preparation method makes up for this technical bottleneck.
  • the purpose of the present invention is to provide a pre-lithiation material, a preparation method thereof, and a lithium battery to solve the problems existing in the prior art.
  • embodiments of the present invention provide a pre-lithiation material, which at least includes a core pre-lithiation material;
  • the pre-lithiation material is a composite of the core pre-lithiation material and a coating material
  • the coating material is one or more combinations of oxide materials, phosphate materials, semiconductor materials, and fast ion conductor materials;
  • the oxide material includes: one or more combinations of aluminum oxide, titanium oxide, magnesium oxide, iron oxide, zinc oxide, niobium oxide, tantalum oxide, and manganese oxide;
  • the phosphate material includes: one or more combinations of aluminum phosphate, lithium phosphate, titanium phosphate, and magnesium phosphate;
  • the fast ion conductor material includes one of a garnet type solid electrolyte material, a NASCION type solid electrolyte material, a LISCION solid electrolyte material, a perovskite type solid electrolyte material and derivatives thereof;
  • the semiconductor material includes one or more combinations of Si, InAs, and AlSb;
  • the coating material is uniformly or unevenly coated on the surface of the core pre-lithiation material; the mass ratio of the coating material to the core pre-lithiation material is between 1:1000 and 1:1.
  • the mass ratio of the coating material to the core pre-lithiation material is between 1:1000 and 1:20.
  • the M1 specifically includes one or more of aluminum, magnesium, sodium, potassium, calcium, nickel, cesium, and rubidium;
  • the M2 specifically includes aluminum, titanium, iron, vanadium, tungsten, niobium, tantalum, and zirconium. , Lanthanum, manganese, magnesium, calcium, cobalt, nickel, zinc, barium one or more.
  • the particle size of the pre-lithiation material is 10nm-50um, and the particle shape is one or more of circular, elliptical, flake or polygonal; the delithiation capacity of the pre-lithiation material is 200mAh/g -1000mAh/g, delithiation voltage is 1-6V.
  • the pre-lithiated material is applied to the cell, the reaction occurs in the first week of charging and discharging of becoming (Li s 'M1 t') (Cu x 'M2 y') (O a 'M3 b'), wherein 0 ⁇ s' ⁇ 1, 0 ⁇ t' ⁇ 1, 0 ⁇ x' ⁇ 1, 0 ⁇ y' ⁇ 1, 0 ⁇ b' ⁇ 1, 1 ⁇ a' ⁇ 2, and s', t', x ', y'are not zero at the same time.
  • an embodiment of the present invention provides a preparation method, including:
  • the raw materials of the pre-lithiation material are put into the mixing equipment according to the stoichiometric ratio and uniformly mixed to obtain a mixture; wherein, the raw materials of the pre-lithiation material include the oxidation of Li, Cu, M1, M2, and M3. Compounds, hydroxides, carbonates, phosphates, ammonium salts, organic salts and metal compounds; where M1 is the first metal element, including one or more of alkali metal elements and alkaline earth metal elements; M2 is the second Metal elements include one or more mixtures of alkaline earth metal elements and transition metal elements; M3 is one or more mixtures of F, S, N, Br, and Cl;
  • the mixture into a sintering device for sintering, and the sintering temperature is between 300°C and 1050°C to obtain a semi-finished material;
  • the semi-finished material after the primary crushing is put into a crushing device for crushing to obtain the pre-lithiation material.
  • the mixing equipment includes: one of a double-motion mixer, a three-dimensional mixer, a V-type mixer, a single-cone double-screw mixer, a grooved ribbon mixer, and a horizontal non-gravity mixer;
  • the sintering equipment includes one of a box furnace, a tube furnace, a roller hearth, and a rotary furnace;
  • the crushing equipment includes one of a jaw crusher, a cone crusher, an impact crusher, a hammer crusher, and a roller crusher;
  • the crushing equipment includes: flat jet mill, fluidized bed jet mill, circulating jet mill, impact crusher, expansion crusher, ball mill crusher, high-speed rotary jet mill and high-speed rotary impact mill One of the type crushers;
  • the sintering specifically includes: sintering in an air atmosphere, a vacuum atmosphere, a nitrogen atmosphere, an argon atmosphere, an argon hydrogen atmosphere or an oxygen atmosphere.
  • putting the semi-finished material after the primary crushing into a crushing device for crushing to obtain the pre-lithiation material specifically includes:
  • the primary pre-lithiation material is put into a sintering device for sintering, and the sintering temperature is between 200° C. and 900° C. to obtain the pre-lithiation material.
  • an embodiment of the present invention provides a lithium battery including the pre-lithiation material described in the first aspect.
  • the pre-lithiation material provided by the present invention has stable properties, can greatly improve the capacity of the lithium battery, has a simple preparation method, low environmental requirements, abundant raw materials, and is suitable for large-scale production.
  • FIG. 1 is a flow chart of a method for preparing a pre-lithiation material provided by an embodiment of the present invention
  • FIG. 2 is a flow chart of another method for preparing a pre-lithiation material provided by an embodiment of the present invention.
  • SEM scanning electron microscope
  • FIG. 4 is an X-ray diffraction (XRD) diagram of a pre-lithiation material provided by an embodiment of the present invention
  • Figure 5 is a graph of electrochemical performance of an embodiment of the present invention.
  • the embodiment of the present invention provides a pre-lithiation material, a preparation method thereof, and a lithium battery.
  • M1 is the first metal element, including one or more of alkali metal elements and alkaline earth metal elements; preferably, M1 may specifically include one or more of aluminum, magnesium, sodium, potassium, calcium, nickel, cesium, and rubidium.
  • M2 is the second metal element, including one or more mixtures of alkaline earth metal elements and transition metal elements; preferably, M2 may specifically include aluminum, titanium, iron, vanadium, tungsten, niobium, tantalum, zirconium, lanthanum, One or more of manganese, magnesium, calcium, cobalt, nickel, zinc, and barium; M3 is a mixture of one or more of F, S, N, Br, and Cl.
  • the pre-lithiation material of the present invention can also be composited by the aforementioned core pre-lithiation material and the coating material; wherein, the coating material can include one of oxide materials, phosphate materials, semiconductor materials, fast ion conductor materials or Multiple combinations; oxide materials include one or more combinations of aluminum oxide, titanium oxide, magnesium oxide, iron oxide, zinc oxide, niobium oxide, tantalum oxide, and manganese oxide; phosphate materials include aluminum phosphate, lithium phosphate, and phosphoric acid One or more combinations of titanium and magnesium phosphate; fast ion conductor materials include any of garnet solid electrolyte materials, NASCION solid electrolyte materials, LISCION solid electrolyte materials, perovskite solid electrolyte materials and their derivatives Species; semiconductor materials include one or more combinations of Si, InAs, AlSb.
  • the coating material is uniformly or unevenly coated on the surface of the core prelithiation material; the mass ratio of the coating material to the core prelithiation material is between 1:1000-1:1, preferably 1:1000-1 : Between 20.
  • the particle shape of the pre-lithiation material of the present invention is one or more of round, elliptical, flake or polygonal, and the particle size is 10nm-50um.
  • the delithiation capacity of the pre-lithiated material is 200mAh/g-1000mAh/g, and the delithiation voltage is 1-6V, which is stable in the air.
  • Pre-lithiated material of the present invention is applied to a battery, a reaction occurs in the first week of charging and discharging of becoming (Li s 'M1 t') (Cu x 'M2 y') (O a 'M3 b'), where 0 ⁇ s' ⁇ 1, 0 ⁇ t' ⁇ 1, 0 ⁇ x' ⁇ 1, 0 ⁇ y' ⁇ 1, 0 ⁇ b' ⁇ 1, 1 ⁇ a' ⁇ 2, and s', t', x', y'is not zero at the same time.
  • Fig. 1 the preparation method of the pre-lithiation material is shown in Fig. 1, which can be prepared according to the following steps:
  • Step 110 Put the raw materials of the pre-lithiation material into the mixing equipment according to the stoichiometric ratio for uniform mixing to obtain a mixture;
  • the raw materials of lithiated materials include oxides, hydroxides, carbonates, phosphates, ammonium salts, organic salts, and metal compounds of Li, Cu, M1, M2, and M3 elements; among them, M1, M2, M3 is as described above.
  • the mixing equipment includes one of a double-motion mixer, a three-dimensional mixer, a V-type mixer, a single-cone double-screw mixer, a grooved ribbon mixer, and a horizontal non-gravity mixer.
  • Step 120 Put the mixture into a sintering device for sintering, and the sintering temperature is between 300°C and 1050°C to obtain a semi-finished material;
  • Sintering refers to sintering in air atmosphere, vacuum atmosphere, nitrogen atmosphere, argon atmosphere, argon hydrogen atmosphere or oxygen atmosphere; sintering equipment includes one of box furnace, tube furnace, roller hearth and rotary furnace.
  • Step 130 Put the semi-finished material into the crushing equipment for primary crushing
  • Crushing equipment includes one of jaw crushers, cone crushers, impact crushers, hammer crushers and roller crushers.
  • Step 140 Put the primary crushed semi-finished material into a crushing device for crushing to obtain a pre-lithiation material.
  • Crushing equipment includes flat jet mills, fluidized bed jet mills, circulating jet mills, impact crushers, expansion crushers, ball mills, high-speed rotating jet mills and high-speed rotating impact mills One of them.
  • the general formula of the main components of the prepared pre-lithiation material is (Li s M1 t )(Cu x M2 y )(O a M3 b ). Each component is defined as described above.
  • Step 210 Put the raw materials of the pre-lithiation material into the mixing equipment according to the stoichiometric ratio for uniform mixing to obtain a mixture;
  • Step 220 Put the mixture into a sintering device for sintering, and the sintering temperature is between 300° C. and 1050° C. to obtain a semi-finished material;
  • Step 230 Put the semi-finished material into the crushing equipment for primary crushing
  • Step 240 Put the semi-finished material after the primary crushing into the crushing equipment for crushing to obtain the core pre-lithiation material
  • the general formula of the core prelithiation material is (Li s M1 t )(Cu x M2 y )(O a M3 b ), and the composition is as described above.
  • Step 250 Put the core pre-lithiation material and the coating material in a mixing device or a fusion device in a required ratio for mixing, so as to coat the core pre-lithiation material to obtain a primary pre-lithiation material;
  • Step 260 Put the primary pre-lithiation material into a sintering device for sintering, and the sintering temperature is between 200° C. and 900° C. to obtain the pre-lithiation material.
  • the above preparation method is simple, has low environmental requirements, is rich in raw materials, and is suitable for large-scale production.
  • This embodiment provides a pre-lithiation material Li 1.75 (Cu 0.95 Nb 0.05 )O 2 .
  • the preparation process is to weigh 1um lithium carbonate, 500nm copper oxide, and 500nm niobium oxide materials according to the corresponding stoichiometric ratio.
  • the three raw materials were placed in a V-cone screw mixer for high-speed mixing with a rotation speed of 400 rpm and a mixing time of 1 hour.
  • the mixture was taken out and placed in an atmosphere box furnace for sintering. A nitrogen atmosphere is introduced, and the specific sintering procedure is: room temperature to 800°C, heating rate 5°C/min, heat preservation for 5 hours, and natural cooling.
  • Fig. 5 is a half-cell electrochemical performance test of the pre-lithiated material prepared in this embodiment, and the test result shows that its specific capacity is 300 mAh/g.
  • This embodiment provides a pre-lithiation material Li 1.75 (Cu 0.95 Nb 0.05 )O 2 coated with fast ion conductor material lithium titanium aluminum phosphate (LATP).
  • the core prelithiation material was prepared according to Example 1.
  • the 100nm fast ion conductor material LATP and the pre-lithiation material Li 1.75 (Cu 0.95 Nb 0.05 )O 2 were put into a high-speed fusion machine at a ratio of 1:100, and fusion was carried out for 15 minutes after 2000 rpm.
  • the primary pre-lithiation material is sintered in an air atmosphere at 400° C. to finally obtain the target pre-lithiation material.
  • the X-ray diffraction (XRD) pattern of the material is shown in Figure 2.
  • the electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 340 mAh/g.
  • This embodiment provides a pre-lithiation material Li 1.9 CuO 1.9 F 0.1 .
  • the preparation process is to weigh the lithium carbonate with a particle size of 1 um and the lithium fluoride with a copper oxide of 500 nm and 1 um according to the corresponding stoichiometric ratio.
  • the four raw materials were placed in a V-cone screw mixer for high-speed mixing at a speed of 400 rpm and a mixing time of 1 hour.
  • the mixture was taken out and placed in an atmosphere box furnace for sintering.
  • the sintering procedure is argon atmosphere, room temperature to 950°C, heating rate 5°C/min, holding for 48 hours, and cooling naturally.
  • the semi-finished product is crushed by a jaw crusher, and then crushed by a jet mill to obtain a pre-lithiation material.
  • the electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 695 mAh/g.
  • This embodiment provides a pre-lithiation material Li 1.9 CuO 1.9 F 0.1 coated with alumina material.
  • the core pre-lithiation material Li 1.9 CuO 1.9 F 0.1 was prepared according to Example 3. Put the 10nm alumina material and the pre-lithiated material Li 1.9 CuO 1.9 F 0.1 into a high-speed fusion machine at a ratio of 1:100, and fuse for 15 minutes after 2000 revolutions.
  • the primary pre-lithiation material is sintered at 400° C. in an air atmosphere to finally obtain the pre-lithiation material.
  • the electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 704mAh/g.
  • This embodiment provides a pre-lithiation material Li 1.9 Cu 0.9 Al 0.1 O 1.8 S 0.2 .
  • the preparation process is to weigh 1um lithium carbonate, 500nm copper oxide, 10nm aluminum oxide material, and 500nm lithium sulfide material according to the corresponding stoichiometric ratio.
  • the four raw materials were placed in a V-cone screw mixer for high-speed mixing at a speed of 400 rpm and a mixing time of 1 hour.
  • the mixture was taken out and placed in an atmosphere box furnace for sintering.
  • the sintering procedure is specified as follows: room temperature to 850°C, heating rate 5°C/min, holding for 28 hours, and natural cooling.
  • the semi-finished product is crushed by a jaw crusher, and then crushed by a jet mill to obtain a pre-lithiation material.
  • the electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 353 mAh/g.
  • This embodiment provides a pre-lithiation material Li 1.95 Na 0.05 CuO 1.95 CL 0.05 .
  • the preparation process is to weigh 1um lithium carbonate, 500nm copper oxide, and 1um sodium chloride according to the corresponding stoichiometric ratio.
  • the three raw materials were placed in a V-cone screw mixer for high-speed mixing with a rotation speed of 400 rpm and a mixing time of 1 hour.
  • the mixture was taken out and placed in an atmosphere box furnace for sintering. A nitrogen atmosphere was introduced, and the specific sintering procedure was: room temperature to 900°C, heating rate 5°C/min, holding for 48 hours, and natural cooling.
  • the semi-finished product is crushed by a jaw crusher, and then crushed by a jet mill to obtain a pre-lithiation material.
  • the electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 250 mAh/g.
  • the pre-lithiation material provided by the invention can greatly improve the capacity of the lithium battery, and has a simple preparation method, low environmental requirements, stable room temperature, abundant raw materials, and is suitable for large-scale production. When applied to lithium batteries, it can power various devices or devices such as mobile phones, tablet computers, digital cameras, power battery packs, and electric vehicles.

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Abstract

Disclosed are a prelithiation material, a preparation method thereof, and a lithium battery. The prelithiation material comprises at least a core prelithiation material, wherein a general formula of the core prelithiation material is (LisM1t)(CuxM2y)(OaM3b), x + y = 1, a + b = 2; 1 < s ≤ 2, 0 ≤ t ≤ 1, 0.5 ≤ x ≤ 1, 0 ≤ y ≤ 0.5; 0 ≤ b ≤ 2; 0 < t + y + b, wherein M1 is a first metal element and comprises a mixture of one or more of alkali metal elements and alkaline earth metal elements, M2 is a second metal element and comprises a mixture of one or more alkaline earth metal elements and transition metal elements, and M3 is a mixture of one or more of F, S, N, Br, and Cl.

Description

一种预锂化材料及其制备方法和锂电池Pre-lithiation material, preparation method thereof and lithium battery
本申请要求于2019年01月25日提交中国专利局、申请号为201910072281.4、发明名称为“一种预锂化材料及其制备方法和锂电池”的中国专利申请的优先权。This application claims the priority of a Chinese patent application submitted to the Chinese Patent Office on January 25, 2019, with the application number 201910072281.4, and the title of the invention "a pre-lithiation material and its preparation method and lithium battery".
技术领域Technical field
本发明涉及锂电池材料技术领域，尤其涉及一种预锂化材料及其制备方法及锂电池。The invention relates to the technical field of lithium battery materials, in particular to a pre-lithiation material, a preparation method thereof, and a lithium battery.
背景技术Background technique
锂离子电池因具有输出电压高、能量密度高、循环寿命长、安全性能好、无记忆效应等特点，作为主要的储能器件成功应用于移动电源领域。为了进一步满足电网储能、电动汽车以及消费类电子产品对储能器件的需求，更长循环寿命、安全性更好、能量密度更高的电极材料以及锂电池体系成为研究热点。Because of its high output voltage, high energy density, long cycle life, good safety performance, and no memory effect, lithium-ion batteries have been successfully applied to the field of mobile power supplies as the main energy storage device. In order to further meet the demand for energy storage devices for grid energy storage, electric vehicles and consumer electronics, electrode materials and lithium battery systems with longer cycle life, better safety, and higher energy density have become research hotspots.
目前商业化锂离子电池负极主要采用石墨材料，石墨材料的理论容量在372mAh/g，限制了锂离子电池整体的比容量。用更高理论容量的合金负极材料逐渐代替石墨材料成为趋势。然而大多数高比容量负极材料普遍存在首周和锂离子发生不可逆反应，从而消耗锂电池中锂源，降低了电池整体比容量。At present, the negative electrode of commercial lithium-ion batteries mainly uses graphite materials. The theoretical capacity of graphite materials is 372mAh/g, which limits the overall specific capacity of lithium-ion batteries. It has become a trend to gradually replace graphite materials with alloy anode materials with higher theoretical capacity. However, most high specific capacity anode materials generally have an irreversible reaction with lithium ions in the first week, which consumes the lithium source in the lithium battery and reduces the overall specific capacity of the battery.
因此解决高比容量的合金负极材料的首周效率低的问题成为关键。其中预锂化技术提出在电池化成首周补充锂离子，成为最有可能的解决方案。然而现有的预锂化技术大部分存在预锂化量难以控制、预锂化量小、存在副反应、对环境要求高、室温不稳定等问题，因此迫切需要提出一种预锂 化材料及其制备方法来弥补这种技术瓶颈。Therefore, solving the problem of low first week efficiency of high specific capacity alloy anode materials becomes the key. Among them, the pre-lithiation technology proposes to replenish lithium ions in the first week of battery formation, which becomes the most possible solution. However, most of the existing prelithiation technologies have problems such as difficult control of the prelithiation amount, small prelithiation amount, side reactions, high environmental requirements, and room temperature instability. Therefore, there is an urgent need to propose a prelithiation material and Its preparation method makes up for this technical bottleneck.
发明内容Summary of the invention
本发明的目的是提供一种预锂化材料及其制备方法和锂电池，用以解决现有技术存在的问题。The purpose of the present invention is to provide a pre-lithiation material, a preparation method thereof, and a lithium battery to solve the problems existing in the prior art.
为实现上述目的，第一方面，本发明实施例提供了一种预锂化材料，至少包括内核预锂化材料；To achieve the foregoing objective, in the first aspect, embodiments of the present invention provide a pre-lithiation material, which at least includes a core pre-lithiation material;
其中，所述内核预锂化材料的通式为(Li sM1 t)(Cu xM2 y)(O aM3 b)，x+y＝1，a+b＝2；1＜s≤2，0≤t≤1，0.5≤x≤1，0≤y≤0.5；0≤b≤2；0＜t+y+b；其中M1为第一金属元素，包括碱金属元素、碱土金属元素的一种或多种混合；M2为第二金属元素，包括碱土金属元素、过渡金属元素的一种或多种混合；M3为F、S、N、Br、Cl的一种或多种混合。 The general formula of the core pre-lithiation material is (Li s M1 t )(Cu x M2 y )(O a M3 b ), x+y=1, a+b=2; 1<s≤2, 0≤t≤1, 0.5≤x≤1, 0≤y≤0.5; 0≤b≤2; 0＜t+y+b; where M1 is the first metal element, including one of alkali metal elements and alkaline earth metal elements One or more mixtures; M2 is the second metal element, including one or more mixtures of alkaline earth metal elements and transition metal elements; M3 is one or more mixtures of F, S, N, Br, and Cl.
优选的，所述预锂化材料由所述内核预锂化材料和包覆材料复合而成；Preferably, the pre-lithiation material is a composite of the core pre-lithiation material and a coating material;
所述包覆材料为氧化物材料、磷酸盐材料、半导体材料、快离子导体材料的一种或多种组合；The coating material is one or more combinations of oxide materials, phosphate materials, semiconductor materials, and fast ion conductor materials;
所述氧化物材料包括：氧化铝、氧化钛、氧化镁、氧化铁、氧化锌、氧化铌、氧化钽、氧化锰的一种或多种组合；The oxide material includes: one or more combinations of aluminum oxide, titanium oxide, magnesium oxide, iron oxide, zinc oxide, niobium oxide, tantalum oxide, and manganese oxide;
所述磷酸盐材料包括：磷酸铝、磷酸锂、磷酸钛、磷酸镁的一种或多种组合；The phosphate material includes: one or more combinations of aluminum phosphate, lithium phosphate, titanium phosphate, and magnesium phosphate;
所述快离子导体材料包括：石榴石型固态电解质材料、NASCION型固态电解质材料、LISCION固态电解质材料、钙钛矿型固态电解质材料及其衍生材料中的一种；The fast ion conductor material includes one of a garnet type solid electrolyte material, a NASCION type solid electrolyte material, a LISCION solid electrolyte material, a perovskite type solid electrolyte material and derivatives thereof;
所述半导体材料包括：Si、InAs、AlSb中的一种或多种组合；The semiconductor material includes one or more combinations of Si, InAs, and AlSb;
所述包覆材料均匀或不均匀的包覆在所述内核预锂化材料的表面；所述包覆材料与所述内核预锂化材料的质量比在1:1000-1:1之间。The coating material is uniformly or unevenly coated on the surface of the core pre-lithiation material; the mass ratio of the coating material to the core pre-lithiation material is between 1:1000 and 1:1.
进一步优选的，所述包覆材料与所述内核预锂化材料的质量比在 1:1000-1:20之间。Further preferably, the mass ratio of the coating material to the core pre-lithiation material is between 1:1000 and 1:20.
优选的，所述M1具体包括铝、镁、钠、钾、钙、镍、铯、铷的一种或多种；所述M2具体包括铝、钛、铁、钒、钨、铌、钽、锆、镧、锰、镁、钙、钴、镍、锌、钡的一种或多种。Preferably, the M1 specifically includes one or more of aluminum, magnesium, sodium, potassium, calcium, nickel, cesium, and rubidium; the M2 specifically includes aluminum, titanium, iron, vanadium, tungsten, niobium, tantalum, and zirconium. , Lanthanum, manganese, magnesium, calcium, cobalt, nickel, zinc, barium one or more.
优选的，所述预锂化材料的粒度为10nm-50um，颗粒性状为圆形、椭圆形、片状或多边形的一种或多种；所述预锂化材料的脱锂容量为200mAh/g-1000mAh/g，脱锂电压为1-6V。Preferably, the particle size of the pre-lithiation material is 10nm-50um, and the particle shape is one or more of circular, elliptical, flake or polygonal; the delithiation capacity of the pre-lithiation material is 200mAh/g -1000mAh/g, delithiation voltage is 1-6V.
优选的，所述预锂化材料应用于电池中，在首周充放电发生反应，化成为(Li s’M1 t’)(Cu x’M2 y’)(O a’M3 b’)，其中0≤s’≤1，0≤t’≤1，0≤x’≤1，0≤y’≤1，0≤b’≤1，1≤a’＜2，并且s’，t’，x’，y’不同时为零。 Preferably, the pre-lithiated material is applied to the cell, the reaction occurs in the first week of charging and discharging of becoming (Li s 'M1 t') (Cu x 'M2 y') (O a 'M3 b'), wherein 0≤s'≤1, 0≤t'≤1, 0≤x'≤1, 0≤y'≤1, 0≤b'≤1, 1≤a'<2, and s', t', x ', y'are not zero at the same time.
第二方面，本发明实施例提供了一种制备方法，包括：In the second aspect, an embodiment of the present invention provides a preparation method, including:
将预锂化材料的原材料，按照化学计量比放入混合设备中进行均匀混合，得到混合物；其中，所述预锂化材料的原材料包括Li、Cu、M1、M2、M3几种元素各自的氧化物、氢氧化物、碳酸盐、磷酸盐、铵盐、有机盐以及金属化合物；其中M1为第一金属元素，包括碱金属元素、碱土金属元素的一种或多种混合；M2为第二金属元素，包括碱土金属元素、过渡金属元素的一种或多种混合；M3为F、S、N、Br、Cl的一种或多种混合；The raw materials of the pre-lithiation material are put into the mixing equipment according to the stoichiometric ratio and uniformly mixed to obtain a mixture; wherein, the raw materials of the pre-lithiation material include the oxidation of Li, Cu, M1, M2, and M3. Compounds, hydroxides, carbonates, phosphates, ammonium salts, organic salts and metal compounds; where M1 is the first metal element, including one or more of alkali metal elements and alkaline earth metal elements; M2 is the second Metal elements include one or more mixtures of alkaline earth metal elements and transition metal elements; M3 is one or more mixtures of F, S, N, Br, and Cl;
将所述混合物放入烧结设备中进行烧结，烧结温度在300℃-1050℃之间，得到半成品料；Put the mixture into a sintering device for sintering, and the sintering temperature is between 300°C and 1050°C to obtain a semi-finished material;
将所述半成品料放入破碎设备进行初级破碎；Put the semi-finished material into the crushing equipment for primary crushing;
将所述初级破碎后的半成品材料投入粉碎设备进行粉碎，得到所述预锂化材料。The semi-finished material after the primary crushing is put into a crushing device for crushing to obtain the pre-lithiation material.
优选的，所述混合设备包括：双运动混合机、三维混合机、V型混合机、单锥双螺旋混合机、槽式螺带混合机和卧式无重力混合机中的一种；Preferably, the mixing equipment includes: one of a double-motion mixer, a three-dimensional mixer, a V-type mixer, a single-cone double-screw mixer, a grooved ribbon mixer, and a horizontal non-gravity mixer;
所述烧结设备包括：箱式炉、管式炉、辊道窖和回转炉中的一种；The sintering equipment includes one of a box furnace, a tube furnace, a roller hearth, and a rotary furnace;
所述破碎设备包括：颚式破碎机、圆锥破碎机、反击式破碎机、锤式破碎机和辊式破碎机中的一种；The crushing equipment includes one of a jaw crusher, a cone crusher, an impact crusher, a hammer crusher, and a roller crusher;
所述粉碎设备包括：扁平式气流粉碎机、流化床式气流粉碎机、循环式气流粉碎机、撞击式破碎机、膨胀式破碎机、球磨粉碎机、高速旋转抛射式粉碎机和高速旋转撞击式粉碎机中的一种；The crushing equipment includes: flat jet mill, fluidized bed jet mill, circulating jet mill, impact crusher, expansion crusher, ball mill crusher, high-speed rotary jet mill and high-speed rotary impact mill One of the type crushers;
所述烧结具体包括：在空气气氛、真空气氛、氮气气氛、氩气气氛、氩氢气氛或氧气气氛下进行烧结。The sintering specifically includes: sintering in an air atmosphere, a vacuum atmosphere, a nitrogen atmosphere, an argon atmosphere, an argon hydrogen atmosphere or an oxygen atmosphere.
优选的，将所述初级破碎后的半成品材料投入粉碎设备进行粉碎，得到所述预锂化材料具体包括：Preferably, putting the semi-finished material after the primary crushing into a crushing device for crushing to obtain the pre-lithiation material specifically includes:
将所述初级破碎后的半成品材料投入粉碎设备进行粉碎，得到内核预锂化材料；Putting the primary crushed semi-finished material into a crushing device for crushing to obtain a core pre-lithiation material;
将所述内核预锂化材料与包覆材料按照所需比例放入混合设备或者融合设备中进行混合，用以对所述内核预锂化材料进行包覆处理，得到初级预锂化材料；Putting the core pre-lithiation material and the coating material in a mixing device or a fusion device in a required ratio for mixing, so as to coat the core pre-lithiation material to obtain a primary pre-lithiation material;
将初级预锂化材料放入烧结设备中进行烧结，烧结温度在200℃-900℃之间，得到所述预锂化材料。The primary pre-lithiation material is put into a sintering device for sintering, and the sintering temperature is between 200° C. and 900° C. to obtain the pre-lithiation material.
第三方面，本发明实施例提供了一种包括上述第一方面所述的预锂化材料的锂电池。In a third aspect, an embodiment of the present invention provides a lithium battery including the pre-lithiation material described in the first aspect.
本发明提供的预锂化材料预锂化材料性质稳定，能够极大的提升了锂电池的容量，其制备方法简单、对环境要求低、原材料丰富、适用于大规模生产。The pre-lithiation material provided by the present invention has stable properties, can greatly improve the capacity of the lithium battery, has a simple preparation method, low environmental requirements, abundant raw materials, and is suitable for large-scale production.
附图说明Description of the drawings
下面通过附图和实施例，对本发明实施例的技术方案做进一步详细描述。The technical solutions of the embodiments of the present invention will be described in further detail below through the accompanying drawings and embodiments.
图1为本发明实施例提供的一种预锂化材料的制备方法流程图；FIG. 1 is a flow chart of a method for preparing a pre-lithiation material provided by an embodiment of the present invention;
图2为本发明实施例提供的另一种预锂化材料的制备方法流程图；2 is a flow chart of another method for preparing a pre-lithiation material provided by an embodiment of the present invention;
图3为本发明实施例提供的预锂化材料的扫描电子显微镜(SEM)图；3 is a scanning electron microscope (SEM) image of a pre-lithiation material provided by an embodiment of the present invention;
图4为本发明实施例提供的预锂化材料的X射线衍射(XRD)图；FIG. 4 is an X-ray diffraction (XRD) diagram of a pre-lithiation material provided by an embodiment of the present invention;
图5为本发明实施例的电化学性能图。Figure 5 is a graph of electrochemical performance of an embodiment of the present invention.
具体实施方式detailed description
本发明实施例提供了一种预锂化材料及其制备方法和锂电池。The embodiment of the present invention provides a pre-lithiation material, a preparation method thereof, and a lithium battery.
本发明的预锂化材料至少包括内核预锂化材料；其中，内核预锂化材料的通式为(Li sM1 t)(Cu xM2 y)(O aM3 b)，x+y＝1，a+b＝2；1＜s≤2，0≤t≤1，0.5≤x≤1，0≤y≤0.5；0≤b≤2；0＜t+y+b。M1为第一金属元素，包括碱金属元素、碱土金属元素的一种或多种混合；优选的，M1可以具体包括铝、镁、钠、钾、钙、镍、铯、铷的一种或多种；M2为第二金属元素，包括碱土金属元素、过渡金属元素的一种或多种混合；优选的，M2可以具体包括铝、钛、铁、钒、钨、铌、钽、锆、镧、锰、镁、钙、钴、镍、锌、钡的一种或多种；M3为F、S、N、Br、Cl的一种或多种混合。 The pre-lithiation material of the present invention includes at least the core pre-lithiation material; wherein the general formula of the core pre-lithiation material is (Li s M1 t )(Cu x M2 y )(O a M3 b ), x+y=1 , A+b=2; 1＜s≤2, 0≤t≤1, 0.5≤x≤1, 0≤y≤0.5; 0≤b≤2; 0＜t+y+b. M1 is the first metal element, including one or more of alkali metal elements and alkaline earth metal elements; preferably, M1 may specifically include one or more of aluminum, magnesium, sodium, potassium, calcium, nickel, cesium, and rubidium. Species; M2 is the second metal element, including one or more mixtures of alkaline earth metal elements and transition metal elements; preferably, M2 may specifically include aluminum, titanium, iron, vanadium, tungsten, niobium, tantalum, zirconium, lanthanum, One or more of manganese, magnesium, calcium, cobalt, nickel, zinc, and barium; M3 is a mixture of one or more of F, S, N, Br, and Cl.
本发明的预锂化材料也可以由上述内核预锂化材料和包覆材料复合而成；其中，包覆材料可以包括氧化物材料、磷酸盐材料、半导体材料、快离子导体材料的一种或多种组合；氧化物材料包括氧化铝、氧化钛、氧化镁、氧化铁、氧化锌、氧化铌、氧化钽、氧化锰的一种或多种组合；磷酸盐材料包括磷酸铝、磷酸锂、磷酸钛、磷酸镁的一种或多种组合；快离子导体材料包括石榴石型固态电解质材料、NASCION型固态电解质材料、LISCION固态电解质材料、钙钛矿型固态电解质材料及其衍生材料中的任一种；半导体材料包括Si、InAs、AlSb中的一种或多种组合。The pre-lithiation material of the present invention can also be composited by the aforementioned core pre-lithiation material and the coating material; wherein, the coating material can include one of oxide materials, phosphate materials, semiconductor materials, fast ion conductor materials or Multiple combinations; oxide materials include one or more combinations of aluminum oxide, titanium oxide, magnesium oxide, iron oxide, zinc oxide, niobium oxide, tantalum oxide, and manganese oxide; phosphate materials include aluminum phosphate, lithium phosphate, and phosphoric acid One or more combinations of titanium and magnesium phosphate; fast ion conductor materials include any of garnet solid electrolyte materials, NASCION solid electrolyte materials, LISCION solid electrolyte materials, perovskite solid electrolyte materials and their derivatives Species; semiconductor materials include one or more combinations of Si, InAs, AlSb.
包覆材料均匀或不均匀的包覆在内核预锂化材料的表面；包覆材料与内核预锂化材料的质量比在1:1000-1:1之间，优选的在1:1000-1:20之间。The coating material is uniformly or unevenly coated on the surface of the core prelithiation material; the mass ratio of the coating material to the core prelithiation material is between 1:1000-1:1, preferably 1:1000-1 : Between 20.
本发明的预锂化材料颗粒性状为圆形、椭圆形、片状或多边形的一种或多种，粒度为10nm-50um。The particle shape of the pre-lithiation material of the present invention is one or more of round, elliptical, flake or polygonal, and the particle size is 10nm-50um.
预锂化材料的脱锂容量为200mAh/g-1000mAh/g，脱锂电压为1-6V，在空气中性质稳定。The delithiation capacity of the pre-lithiated material is 200mAh/g-1000mAh/g, and the delithiation voltage is 1-6V, which is stable in the air.
本发明的预锂化材料应用于电池中，在首周充放电发生反应，化成为(Li s’M1 t’)(Cu x’M2 y’)(O a’M3 b’)，其中0≤s’≤1，0≤t’≤1，0≤x’≤1，0≤y’≤1，0≤b’≤1，1≤a’＜2，并且s’，t’，x’，y’不同时为零。 Pre-lithiated material of the present invention is applied to a battery, a reaction occurs in the first week of charging and discharging of becoming (Li s 'M1 t') (Cu x 'M2 y') (O a 'M3 b'), where 0≤ s'≤1, 0≤t'≤1, 0≤x'≤1, 0≤y'≤1, 0≤b'≤1, 1≤a'＜2, and s', t', x', y'is not zero at the same time.
下面介绍本发明预锂化材料的制备方法。The preparation method of the pre-lithiation material of the present invention is described below.
在一种情况下，预锂化材料的制备方法如图1所示，可以按照如下步骤制备得到：In one case, the preparation method of the pre-lithiation material is shown in Fig. 1, which can be prepared according to the following steps:
步骤110，将预锂化材料的原材料，按照化学计量比放入混合设备中进行均匀混合，得到混合物；Step 110: Put the raw materials of the pre-lithiation material into the mixing equipment according to the stoichiometric ratio for uniform mixing to obtain a mixture;
其中，锂化材料的原材料包括Li、Cu、M1、M2、M3几种元素各自的氧化物、氢氧化物、碳酸盐、磷酸盐、铵盐、有机盐以及金属化合物；其中M1、M2、M3如上述所述。Among them, the raw materials of lithiated materials include oxides, hydroxides, carbonates, phosphates, ammonium salts, organic salts, and metal compounds of Li, Cu, M1, M2, and M3 elements; among them, M1, M2, M3 is as described above.
混合设备包括双运动混合机、三维混合机、V型混合机、单锥双螺旋混合机、槽式螺带混合机和卧式无重力混合机中的一种。The mixing equipment includes one of a double-motion mixer, a three-dimensional mixer, a V-type mixer, a single-cone double-screw mixer, a grooved ribbon mixer, and a horizontal non-gravity mixer.
步骤120，将混合物放入烧结设备中进行烧结，烧结温度在300℃-1050℃之间，得到半成品料；Step 120: Put the mixture into a sintering device for sintering, and the sintering temperature is between 300°C and 1050°C to obtain a semi-finished material;
烧结是指在空气气氛、真空气氛、氮气气氛、氩气气氛、氩氢气氛或氧气气氛下进行烧结；烧结设备包括箱式炉、管式炉、辊道窖和回转炉中的一种。Sintering refers to sintering in air atmosphere, vacuum atmosphere, nitrogen atmosphere, argon atmosphere, argon hydrogen atmosphere or oxygen atmosphere; sintering equipment includes one of box furnace, tube furnace, roller hearth and rotary furnace.
步骤130，将半成品料放入破碎设备进行初级破碎；Step 130: Put the semi-finished material into the crushing equipment for primary crushing;
破碎设备包括颚式破碎机、圆锥破碎机、反击式破碎机、锤式破碎机和辊式破碎机中的一种。Crushing equipment includes one of jaw crushers, cone crushers, impact crushers, hammer crushers and roller crushers.
步骤140，将初级破碎后的半成品材料投入粉碎设备进行粉碎，得到预锂化材料。Step 140: Put the primary crushed semi-finished material into a crushing device for crushing to obtain a pre-lithiation material.
粉碎设备包括扁平式气流粉碎机、流化床式气流粉碎机、循环式气流粉碎机、撞击式破碎机、膨胀式破碎机、球磨粉碎机、高速旋转抛射式粉碎机和高速旋转撞击式粉碎机中的一种。Crushing equipment includes flat jet mills, fluidized bed jet mills, circulating jet mills, impact crushers, expansion crushers, ball mills, high-speed rotating jet mills and high-speed rotating impact mills One of them.
制得的预锂化材料主要成分的通式为(Li sM1 t)(Cu xM2 y)(O aM3 b)。各组分限定如前述所述。 The general formula of the main components of the prepared pre-lithiation material is (Li s M1 t )(Cu x M2 y )(O a M3 b ). Each component is defined as described above.
在另一种情况下，预锂化材料的制备方法如图1所示，可以按照如下步骤制备得到：In another case, the preparation method of the pre-lithiation material is shown in Figure 1, which can be prepared according to the following steps:
步骤210，将预锂化材料的原材料，按照化学计量比放入混合设备中进行均匀混合，得到混合物；Step 210: Put the raw materials of the pre-lithiation material into the mixing equipment according to the stoichiometric ratio for uniform mixing to obtain a mixture;
步骤220，将混合物放入烧结设备中进行烧结，烧结温度在300℃-1050℃之间，得到半成品料；Step 220: Put the mixture into a sintering device for sintering, and the sintering temperature is between 300° C. and 1050° C. to obtain a semi-finished material;
步骤230，将半成品料放入破碎设备进行初级破碎；Step 230: Put the semi-finished material into the crushing equipment for primary crushing;
步骤240，将初级破碎后的半成品材料投入粉碎设备进行粉碎，得到内核预锂化材料；Step 240: Put the semi-finished material after the primary crushing into the crushing equipment for crushing to obtain the core pre-lithiation material;
内核预锂化材料的通式为(Li sM1 t)(Cu xM2 y)(O aM3 b)，组分如上所述。 The general formula of the core prelithiation material is (Li s M1 t )(Cu x M2 y )(O a M3 b ), and the composition is as described above.
步骤250，将内核预锂化材料与包覆材料按照所需比例放入混合设备或者融合设备中进行混合，用以对内核预锂化材料进行包覆处理，得到初级预锂化材料；Step 250: Put the core pre-lithiation material and the coating material in a mixing device or a fusion device in a required ratio for mixing, so as to coat the core pre-lithiation material to obtain a primary pre-lithiation material;
步骤260，将初级预锂化材料放入烧结设备中进行烧结，烧结温度在200℃-900℃之间，得到预锂化材料。Step 260: Put the primary pre-lithiation material into a sintering device for sintering, and the sintering temperature is between 200° C. and 900° C. to obtain the pre-lithiation material.
上述制备方法简单、对环境要求低、原材料丰富、适用于大规模生产。The above preparation method is simple, has low environmental requirements, is rich in raw materials, and is suitable for large-scale production.
实施例1Example 1
本实施例提供了一种预锂化材料Li 1.75(Cu 0.95Nb 0.05)O 2。其制备过程是按照相应的化学计量比称量粒度为1um的碳酸锂、500nm的氧化铜、500nm的氧化铌材料。将三种原材料放置于V锥形螺旋混合机中高速混合，转速 为400rpm，混合时间为1小时。取出混合物，放置于气氛箱式炉中进行烧结。通入氮气气氛，烧结的具体程序为：室温到800℃，升温速率5℃/min，保温5小时，自然降温。将烧结之后半成品利用颚式破碎机进行破碎，再经过气流粉碎机进行粉碎，得到预锂化材料。其SEM图如图3所示，XRD谱如图4所示。图5为本实施例所制备的预锂化材料进行半电池电化学性能测试，测试结果其比容量为300mAh/g。 This embodiment provides a pre-lithiation material Li 1.75 (Cu 0.95 Nb 0.05 )O 2 . The preparation process is to weigh 1um lithium carbonate, 500nm copper oxide, and 500nm niobium oxide materials according to the corresponding stoichiometric ratio. The three raw materials were placed in a V-cone screw mixer for high-speed mixing with a rotation speed of 400 rpm and a mixing time of 1 hour. The mixture was taken out and placed in an atmosphere box furnace for sintering. A nitrogen atmosphere is introduced, and the specific sintering procedure is: room temperature to 800°C, heating rate 5°C/min, heat preservation for 5 hours, and natural cooling. After sintering, the semi-finished product is crushed by a jaw crusher, and then crushed by a jet mill to obtain a pre-lithiation material. The SEM image is shown in Figure 3, and the XRD spectrum is shown in Figure 4. Fig. 5 is a half-cell electrochemical performance test of the pre-lithiated material prepared in this embodiment, and the test result shows that its specific capacity is 300 mAh/g.
实施例2Example 2
本实施例提供了一种包覆快离子导体材料磷酸钛铝锂(LATP)的预锂化材料Li 1.75(Cu 0.95Nb 0.05)O 2。内核预锂化材料按照实施例1所制备。将100nm快离子导体材料LATP和预锂化材料Li 1.75(Cu 0.95Nb 0.05)O 2按照1：100比例放入高速融合机，2000rpm之后，15分钟进行融合。将初级预锂化材料在空气气氛下，400℃烧结，最终得到目标预锂化材料。材料的X射线衍射(XRD)图如图2所示。本实施例所制备的预锂化材料进行的半电池电化学性能测试，测试结果其比容量为340mAh/g。 This embodiment provides a pre-lithiation material Li 1.75 (Cu 0.95 Nb 0.05 )O 2 coated with fast ion conductor material lithium titanium aluminum phosphate (LATP). The core prelithiation material was prepared according to Example 1. The 100nm fast ion conductor material LATP and the pre-lithiation material Li 1.75 (Cu 0.95 Nb 0.05 )O 2 were put into a high-speed fusion machine at a ratio of 1:100, and fusion was carried out for 15 minutes after 2000 rpm. The primary pre-lithiation material is sintered in an air atmosphere at 400° C. to finally obtain the target pre-lithiation material. The X-ray diffraction (XRD) pattern of the material is shown in Figure 2. The electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 340 mAh/g.
实施例3Example 3
本实施例提供了一种预锂化材料Li 1.9CuO 1.9F 0.1。其制备过程是按照相应的化学计量比称量粒度为1um的碳酸锂、500nm的氧化铜1um的氟化锂材料。将四种原材料放置于V锥形螺旋混合机中高速混合，转速为400rpm，混合时间为1小时。取出混合物，放置于气氛箱式炉中进行烧结。通入氩气气氛，烧结的具体程序为：室温到950℃，升温速率5℃/min，保温48小时，自然降温。将烧结之后半成品利用颚式破碎机进行破碎，再经过气流粉碎机进行粉碎，得到预锂化材料。本实施例所制备的预锂化材料进行的半电池电化学性能测试，测试结果其比容量为695mAh/g。 This embodiment provides a pre-lithiation material Li 1.9 CuO 1.9 F 0.1 . The preparation process is to weigh the lithium carbonate with a particle size of 1 um and the lithium fluoride with a copper oxide of 500 nm and 1 um according to the corresponding stoichiometric ratio. The four raw materials were placed in a V-cone screw mixer for high-speed mixing at a speed of 400 rpm and a mixing time of 1 hour. The mixture was taken out and placed in an atmosphere box furnace for sintering. The sintering procedure is argon atmosphere, room temperature to 950°C, heating rate 5°C/min, holding for 48 hours, and cooling naturally. After sintering, the semi-finished product is crushed by a jaw crusher, and then crushed by a jet mill to obtain a pre-lithiation material. The electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 695 mAh/g.
实施例4Example 4
本实施例提供了一种包覆氧化铝材料的预锂化材料Li 1.9CuO 1.9F 0.1。内核预锂化材料Li 1.9CuO 1.9F 0.1按照实施例3制备。将10nm氧化铝材料和预锂化材料Li 1.9CuO 1.9F 0.1按照1：100比例放入高速融合机，2000转之后，15分钟进行融合。将初级预锂化材料在空气气氛下，400℃烧结，最终得到预锂化材料。本实施例所制备的预锂化材料进行的半电池电化学性能测试，测试结果其比容量为704mAh/g。 This embodiment provides a pre-lithiation material Li 1.9 CuO 1.9 F 0.1 coated with alumina material. The core pre-lithiation material Li 1.9 CuO 1.9 F 0.1 was prepared according to Example 3. Put the 10nm alumina material and the pre-lithiated material Li 1.9 CuO 1.9 F 0.1 into a high-speed fusion machine at a ratio of 1:100, and fuse for 15 minutes after 2000 revolutions. The primary pre-lithiation material is sintered at 400° C. in an air atmosphere to finally obtain the pre-lithiation material. The electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 704mAh/g.
实施例5Example 5
本实施例提供了一种预锂化材料Li 1.9Cu 0.9Al 0.1O 1.8S 0.2。其制备过程是按照相应的化学计量比称量粒度为1um的碳酸锂、500nm的氧化铜、10nm的氧化铝材料、500nm的硫化锂材料。将四种原材料放置于V锥形螺旋混合机中高速混合，转速为400rpm，混合时间为1小时。取出混合物，放置于气氛箱式炉中进行烧结。通入氩气气氛，烧结的具体程序为：室温到850℃，升温速率5℃/min，保温28小时，自然降温。将烧结之后半成品利用颚式破碎机进行破碎，再经过气流粉碎机进行粉碎，得到预锂化材料。本实施例所制备的预锂化材料进行的半电池电化学性能测试，测试结果其比容量为353mAh/g。 This embodiment provides a pre-lithiation material Li 1.9 Cu 0.9 Al 0.1 O 1.8 S 0.2 . The preparation process is to weigh 1um lithium carbonate, 500nm copper oxide, 10nm aluminum oxide material, and 500nm lithium sulfide material according to the corresponding stoichiometric ratio. The four raw materials were placed in a V-cone screw mixer for high-speed mixing at a speed of 400 rpm and a mixing time of 1 hour. The mixture was taken out and placed in an atmosphere box furnace for sintering. The sintering procedure is specified as follows: room temperature to 850°C, heating rate 5°C/min, holding for 28 hours, and natural cooling. After sintering, the semi-finished product is crushed by a jaw crusher, and then crushed by a jet mill to obtain a pre-lithiation material. The electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 353 mAh/g.
实施例6Example 6
本实施例提供了一种预锂化材料Li 1.95Na 0.05CuO 1.95CL 0.05。其制备过程是按照相应的化学计量比称量粒度为1um的碳酸锂、500nm的氧化铜、1um的氯化钠。将三种原材料放置于V锥形螺旋混合机中高速混合，转速为400rpm，混合时间为1小时。取出混合物，放置于气氛箱式炉中进行烧结。通入氮气气氛，烧结的具体程序为：室温到900℃，升温速率5℃/min，保温48小时，自然降温。将烧结之后半成品利用颚式破碎机进行破碎，再经 过气流粉碎机进行粉碎，得到预锂化材料。本实施例所制备的预锂化材料进行的半电池电化学性能测试，测试结果其比容量为250mAh/g。 This embodiment provides a pre-lithiation material Li 1.95 Na 0.05 CuO 1.95 CL 0.05 . The preparation process is to weigh 1um lithium carbonate, 500nm copper oxide, and 1um sodium chloride according to the corresponding stoichiometric ratio. The three raw materials were placed in a V-cone screw mixer for high-speed mixing with a rotation speed of 400 rpm and a mixing time of 1 hour. The mixture was taken out and placed in an atmosphere box furnace for sintering. A nitrogen atmosphere was introduced, and the specific sintering procedure was: room temperature to 900°C, heating rate 5°C/min, holding for 48 hours, and natural cooling. After sintering, the semi-finished product is crushed by a jaw crusher, and then crushed by a jet mill to obtain a pre-lithiation material. The electrochemical performance test of the half-cell of the pre-lithiated material prepared in this example showed that its specific capacity was 250 mAh/g.
本发明提供的预锂化材料能够极大的提升了锂电池的容量，其制备方法简单、对环境要求低、室温稳定、原材料丰富、适用于大规模生产。将其应用于锂电池中，可以为手机、平板电脑、数码相机、动力电池组、电动车等各种设备或装置供电。The pre-lithiation material provided by the invention can greatly improve the capacity of the lithium battery, and has a simple preparation method, low environmental requirements, stable room temperature, abundant raw materials, and is suitable for large-scale production. When applied to lithium batteries, it can power various devices or devices such as mobile phones, tablet computers, digital cameras, power battery packs, and electric vehicles.
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The specific embodiments described above further describe the purpose, technical solutions and beneficial effects of the present invention in further detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the scope of the present invention. The protection scope, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

  1. 一种预锂化材料，其特征在于，所述预锂化材料至少包括内核预锂化材料；A pre-lithiation material, characterized in that the pre-lithiation material includes at least a core pre-lithiation material;
    其中，所述内核预锂化材料的通式为(Li sM1 t)(Cu xM2 y)(O aM3 b)，x+y＝1，a+b＝2；1＜s≤2，0≤t≤1，0.5≤x≤1，0≤y≤0.5；0≤b≤2；0＜t+y+b；其中M1为第一金属元素，包括碱金属元素、碱土金属元素的一种或多种混合；M2为第二金属元素，包括碱土金属元素、过渡金属元素的一种或多种混合；M3为F、S、N、Br、Cl的一种或多种混合。 The general formula of the core pre-lithiation material is (Li s M1 t )(Cu x M2 y )(O a M3 b ), x+y=1, a+b=2; 1<s≤2, 0≤t≤1, 0.5≤x≤1, 0≤y≤0.5; 0≤b≤2; 0＜t+y+b; where M1 is the first metal element, including one of alkali metal elements and alkaline earth metal elements One or more mixtures; M2 is the second metal element, including one or more mixtures of alkaline earth metal elements and transition metal elements; M3 is one or more mixtures of F, S, N, Br, and Cl.
  2. 根据权利要求1所述的预锂化材料，其特征在于，所述预锂化材料由所述内核预锂化材料和包覆材料复合而成；The pre-lithiation material according to claim 1, wherein the pre-lithiation material is a composite of the core pre-lithiation material and a coating material;
    所述包覆材料为氧化物材料、磷酸盐材料、半导体材料、快离子导体材料的一种或多种组合；The coating material is one or more combinations of oxide materials, phosphate materials, semiconductor materials, and fast ion conductor materials;
    所述氧化物材料包括：氧化铝、氧化钛、氧化镁、氧化铁、氧化锌、氧化铌、氧化钽、氧化锰的一种或多种组合；The oxide material includes: one or more combinations of aluminum oxide, titanium oxide, magnesium oxide, iron oxide, zinc oxide, niobium oxide, tantalum oxide, and manganese oxide;
    所述磷酸盐材料包括：磷酸铝、磷酸锂、磷酸钛、磷酸镁的一种或多种组合；The phosphate material includes: one or more combinations of aluminum phosphate, lithium phosphate, titanium phosphate, and magnesium phosphate;
    所述快离子导体材料包括：石榴石型固态电解质材料、NASCION型固态电解质材料、LISCION固态电解质材料、钙钛矿型固态电解质材料及其衍生材料中的一种；The fast ion conductor material includes one of a garnet type solid electrolyte material, a NASCION type solid electrolyte material, a LISCION solid electrolyte material, a perovskite type solid electrolyte material and derivatives thereof;
    所述半导体材料包括：Si、InAs、AlSb中的一种或多种组合；The semiconductor material includes one or more combinations of Si, InAs, and AlSb;
    所述包覆材料均匀或不均匀的包覆在所述内核预锂化材料的表面；所述包覆材料与所述内核预锂化材料的质量比在1:1000-1:1之间。The coating material is uniformly or unevenly coated on the surface of the core pre-lithiation material; the mass ratio of the coating material to the core pre-lithiation material is between 1:1000 and 1:1.
  3. 根据权利要求2所述的预锂化材料，其特征在于，所述包覆材料与所述内核预锂化材料的质量比在1:1000-1:20之间。The pre-lithiation material according to claim 2, wherein the mass ratio of the coating material to the core pre-lithiation material is between 1:1000 and 1:20.
  4. 根据权利要求1所述的预锂化材料，其特征在于，所述M1具体包括铝、镁、钠、钾、钙、镍、铯、铷的一种或多种；所述M2具体包括铝、 钛、铁、钒、钨、铌、钽、锆、镧、锰、镁、钙、钴、镍、锌、钡的一种或多种。The pre-lithiation material according to claim 1, wherein the M1 specifically includes one or more of aluminum, magnesium, sodium, potassium, calcium, nickel, cesium, and rubidium; and the M2 specifically includes aluminum, One or more of titanium, iron, vanadium, tungsten, niobium, tantalum, zirconium, lanthanum, manganese, magnesium, calcium, cobalt, nickel, zinc, and barium.
  5. 根据权利要求1所述的预锂化材料，其特征在于，所述预锂化材料的粒度为10nm-50um，颗粒性状为圆形、椭圆形、片状或多边形的一种或多种；所述预锂化材料的脱锂容量为200mAh/g-1000mAh/g，脱锂电压为1-6V。The pre-lithiation material of claim 1, wherein the particle size of the pre-lithiation material is 10nm-50um, and the particle shape is one or more of circular, elliptical, flake or polygonal; The delithiation capacity of the pre-lithiation material is 200 mAh/g-1000 mAh/g, and the delithiation voltage is 1-6V.
  6. 根据权利要求1所述的预锂化材料，其特征在于，The pre-lithiation material according to claim 1, wherein:
    所述预锂化材料应用于电池中，在首周充放电发生反应，化成为(Li s’M1 t’)(Cu x’M2 y’)(O a’M3 b’)，其中0≤s’≤1，0≤t’≤1，0≤x’≤1，0≤y’≤1，0≤b’≤1，1≤a’＜2，并且s’，t’，x’，y’不同时为零。 The pre-lithiated material is applied to the cell, the reaction occurs in the first week of charging and discharging of becoming (Li s 'M1 t') (Cu x 'M2 y') (O a 'M3 b'), wherein 0≤s '≤1, 0≤t'≤1, 0≤x'≤1, 0≤y'≤1, 0≤b'≤1, 1≤a'＜2, and s', t', x', y 'Not zero at the same time.
  7. 一种预锂化材料的制备方法，其特征在于，所述制备方法包括：A preparation method of prelithiation material, characterized in that, the preparation method comprises:
    将预锂化材料的原材料，按照化学计量比放入混合设备中进行均匀混合，得到混合物；其中，所述预锂化材料的原材料包括Li、Cu、M1、M2、M3几种元素各自的氧化物、氢氧化物、碳酸盐、磷酸盐、铵盐、有机盐以及金属化合物；其中M1为第一金属元素，包括碱金属元素、碱土金属元素的一种或多种混合；M2为第二金属元素，包括碱土金属元素、过渡金属元素的一种或多种混合；M3为F、S、N、Br、Cl的一种或多种混合；The raw materials of the pre-lithiation material are put into the mixing equipment according to the stoichiometric ratio and uniformly mixed to obtain a mixture; wherein, the raw materials of the pre-lithiation material include the oxidation of Li, Cu, M1, M2, and M3. Compounds, hydroxides, carbonates, phosphates, ammonium salts, organic salts and metal compounds; wherein M1 is the first metal element, including one or more of alkali metal elements and alkaline earth metal elements; M2 is the second Metal elements include one or more mixtures of alkaline earth metal elements and transition metal elements; M3 is one or more mixtures of F, S, N, Br, and Cl;
    将所述混合物放入烧结设备中进行烧结，烧结温度在300℃-1050℃之间，得到半成品料；Put the mixture into a sintering device for sintering, and the sintering temperature is between 300°C and 1050°C to obtain a semi-finished material;
    将所述半成品料放入破碎设备进行初级破碎；Put the semi-finished material into the crushing equipment for primary crushing;
    将所述初级破碎后的半成品材料投入粉碎设备进行粉碎，得到所述预锂化材料。The semi-finished material after the primary crushing is put into a crushing device for crushing to obtain the pre-lithiation material.
  8. 根据权利要求7所述的制备方法，其特征在于，The preparation method according to claim 7, wherein:
    所述混合设备包括：双运动混合机、三维混合机、V型混合机、单锥双螺旋混合机、槽式螺带混合机和卧式无重力混合机中的一种；The mixing equipment includes: one of a double-motion mixer, a three-dimensional mixer, a V-type mixer, a single-cone double-screw mixer, a trough ribbon mixer, and a horizontal zero-gravity mixer;
    所述烧结设备包括：箱式炉、管式炉、辊道窖和回转炉中的一种；The sintering equipment includes one of a box furnace, a tube furnace, a roller hearth, and a rotary furnace;
    所述破碎设备包括：颚式破碎机、圆锥破碎机、反击式破碎机、锤式破碎机和辊式破碎机中的一种；The crushing equipment includes one of a jaw crusher, a cone crusher, an impact crusher, a hammer crusher, and a roller crusher;
    所述粉碎设备包括：扁平式气流粉碎机、流化床式气流粉碎机、循环式气流粉碎机、撞击式破碎机、膨胀式破碎机、球磨粉碎机、高速旋转抛射式粉碎机和高速旋转撞击式粉碎机中的一种；The crushing equipment includes: flat jet mill, fluidized bed jet mill, circulating jet mill, impact crusher, expansion crusher, ball mill crusher, high-speed rotary jet mill and high-speed rotary impact mill One of the type crushers;
    所述烧结具体包括：在空气气氛、真空气氛、氮气气氛、氩气气氛、氩氢气氛或氧气气氛下进行烧结。The sintering specifically includes: sintering in an air atmosphere, a vacuum atmosphere, a nitrogen atmosphere, an argon atmosphere, an argon hydrogen atmosphere or an oxygen atmosphere.
  9. 根据权利要求7所述的预锂化材料的制备方法，其特征在于，将所述初级破碎后的半成品材料投入粉碎设备进行粉碎，得到所述预锂化材料具体包括：The method for preparing a pre-lithiation material according to claim 7, characterized in that, putting the preliminary crushed semi-finished material into a crushing device for crushing to obtain the pre-lithiation material specifically comprises:
    将所述初级破碎后的半成品材料投入粉碎设备进行粉碎，得到内核预锂化材料；Putting the primary crushed semi-finished material into a crushing device for crushing to obtain a core pre-lithiation material;
    将所述内核预锂化材料与包覆材料按照所需比例放入混合设备或者融合设备中进行混合，用以对所述内核预锂化材料进行包覆处理，得到初级预锂化材料；Putting the core pre-lithiation material and the coating material into a mixing device or a fusion device in a required ratio for mixing, so as to coat the core pre-lithiation material to obtain a primary pre-lithiation material;
    将初级预锂化材料放入烧结设备中进行烧结，烧结温度在200℃-900℃之间，得到所述预锂化材料。The primary pre-lithiation material is put into a sintering device for sintering, and the sintering temperature is between 200° C. and 900° C. to obtain the pre-lithiation material.
  10. 一种包括上述权利要求1-6任一所述的预锂化材料的锂电池。A lithium battery comprising the pre-lithiation material according to any one of claims 1-6.
PCT/CN2019/088253 2019-01-25 2019-05-24 Prelithiation material, preparation method thereof, and lithium battery WO2020151143A1 (en)

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