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CN119400813B - NCMA quaternary positive electrode material, preparation method thereof and all-solid-state battery - Google Patents

NCMA quaternary positive electrode material, preparation method thereof and all-solid-state battery

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CN119400813B
CN119400813B CN202411291554.1A CN202411291554A CN119400813B CN 119400813 B CN119400813 B CN 119400813B CN 202411291554 A CN202411291554 A CN 202411291554A CN 119400813 B CN119400813 B CN 119400813B
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ncma
cathode material
ncma quaternary
positive electrode
quaternary cathode
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杜建国
张健
罗广求
殷立勇
何少平
赵珊珊
郑见杰
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CETC 18 Research Institute
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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Abstract

本发明公开了一种NCMA四元正极材料及其制备方法与全固态电池，制备方法分为三个步骤：步骤1，采用共沉淀法制备NCMA前驱体；步骤2，采用固相烧结法(一次焙烧)制备放射状NCMA四元正极材料；步骤3，对制备的放射状NCMA四元正极材料进行酸式磷酸盐附着和烧结(二次焙烧)，得到酸式磷酸盐附着后的放射状NCMA四元正极材料。本发明制备的NCMA四元正极材料具备良好的结构稳定性，与硫化物电解质的界面形容性良好，可在硫化物电解质全固态电池体系中，将NCMA四元正极材料的高放电比容量以及稳定的循环寿命等优势进行有效地发挥。为实现高镍系正极材料在硫化物电解质全固态电池体系中的普遍应用提供了有效方案。

This invention discloses an NCMA quaternary cathode material, its preparation method, and an all-solid-state battery. The preparation method consists of three steps: Step 1, preparing an NCMA precursor using a co-precipitation method; Step 2, preparing a radial NCMA quaternary cathode material using a solid-state sintering method (one-time calcination); Step 3, subjecting the prepared radial NCMA quaternary cathode material to acid phosphate attachment and sintering (secondary calcination) to obtain an acid phosphate-attached radial NCMA quaternary cathode material. The NCMA quaternary cathode material prepared by this invention possesses good structural stability and excellent interfacial characteristics with sulfide electrolytes. In sulfide electrolyte all-solid-state battery systems, the high discharge specific capacity and stable cycle life advantages of NCMA quaternary cathode materials can be effectively utilized. This provides an effective solution for the widespread application of high-nickel cathode materials in sulfide electrolyte all-solid-state battery systems.

Description

NCMA quaternary positive electrode material, preparation method thereof and all-solid-state battery
Technical Field
The invention belongs to the technical field of positive electrode materials, and particularly relates to NCMA quaternary positive electrode materials, a preparation method thereof and an all-solid-state battery.
Background
The all-solid-state lithium battery is hopeful to solve the safety problem of the traditional lithium battery due to the adoption of nonflammable solid electrolyte, meanwhile, the battery structure is simplified, the design of higher specific energy of the battery can be realized, and the lithium battery has attracted wide attention in recent years.
The electrical properties of all-solid-state lithium batteries are closely related to the solid-state electrolyte, the positive electrode material, and the interfacial properties of both. Sulfides are considered to be very potential solid state electrolytes for all solid state lithium batteries by virtue of their high ionic conductivity (up to 10 -2S cm-1 f at room temperature) comparable to that of liquid electrolytes. In addition, the search for positive electrode materials suitable for use in sulfide electrolyte solid state battery systems is also particularly important for constructing all-solid state lithium batteries with high specific energy and long life. Among them, the high nickel material, especially the quaternary positive electrode material LiNi xCoyMnzAl1-x-y-zO2 (NCMA), is considered to have great application potential in sulfide electrolyte all-solid-state battery systems due to its advantages of high voltage, high specific capacity, long life characteristics and thermal stability over the conventional ternary materials. However, the quaternary positive electrode material has far less electrical performance in an all-solid-state lithium battery than in a liquid lithium ion battery due to severe deterioration and failure of the quaternary positive electrode material/sulfide electrolyte interface during charge and discharge.
During the battery preparation or charge-discharge cycle, due to the difference of chemical potential and electrochemical potential, side reactions can occur between the quaternary positive electrode material and sulfide electrolyte, forming a high-impedance solid/solid interface layer, which impedes the transmission of Li +. In addition, the quaternary positive electrode material has strong surface oxidizing property and extremely poor compatibility with sulfide electrolyte, and can seriously reduce interface stability. The traditional positive electrode material is formed by stacking disordered primary particles, and serious stress concentration is generated in the repeated Li + deintercalation process, so that the material is seriously cracked after long circulation, and the contact failure among the material particles is caused.
For example, a CN 111640928A NCMA quaternary system material, a preparation method thereof, a lithium battery anode material and a lithium battery take NCMA as a substrate, and the coated quaternary anode material is obtained by coating Co 3O4 and V 2O5 metal oxides, so that the cost is high, the process steps are more, the capacity is not high enough after electrochemical testing, the cycle performance is poor, and the industrial production is not facilitated.
Disclosure of Invention
The invention mainly aims to provide NCMA quaternary positive electrode material, a preparation method thereof and an all-solid-state battery, so as to solve the problem that the positive electrode material in the prior art is poor in electrical performance in a sulfide electrolyte solid-state battery system.
The invention is realized in such a way that a NCMA quaternary positive electrode material preparation method comprises the following steps:
step 1, preparing NCMA precursor by adopting a coprecipitation method;
Step 2, preparing a radial NCMA quaternary positive electrode material by adopting solid phase one-time roasting;
and 3, carrying out acid phosphate adhesion and secondary roasting on the prepared radial NCMA quaternary positive electrode material to obtain the radial NCMA quaternary positive electrode material after acid phosphate adhesion.
The chemical formula of the NCMA quaternary positive electrode material is LiNi wCoxMnyAlzO2, wherein w is more than or equal to 0.88 and less than or equal to 0.95,0.03, x is more than or equal to 0.06,0.01 and less than or equal to y is more than or equal to 0.03,0.01 and less than or equal to z is more than or equal to 0.03, and w+x+y+z=1.
The mass ratio of NCMA quaternary positive electrode material to acid phosphate is 0.001-0.05:1, and the acid phosphate is Zr (HPO 4)2·H2 O).
The thickness of the coating layer of the radial NCMA quaternary positive electrode material is 10-50 nm.
In the step 3, the temperature of the second roasting is 400-600 ℃, the time of the second roasting is 5-10 h, and the second roasting is performed in an oxygen atmosphere.
The preparation method comprises the steps of mixing NCMA precursor, liOH and a directional growth inducer to obtain a mixture, roasting the mixture for the first time to obtain a material after primary roasting, cooling and crushing the material after primary roasting to obtain a radial NCMA quaternary positive electrode material with the particle size of 6-20 mu m, wherein the molar ratio of NCMA precursor to LiOH to the directional growth inducer is 1:1-1.06:0.001-0.01.
The directional growth inducer is WO 3.
The mixing is dry mixing, the temperature of the first roasting is 700-850 ℃, the time of the first roasting is 10-20 h, and the first roasting is performed in an oxygen atmosphere.
NCMA quaternary positive electrode materials prepared by the preparation method.
An all-solid-state battery employing the NCMA quaternary positive electrode material described above.
The quaternary positive electrode material with the radial structure has the advantages and technical effects that the quaternary positive electrode material with the radial structure prepared by the invention improves the failure of the quaternary positive electrode material/sulfide electrolyte interface, namely, the growth of primary particles of the quaternary positive electrode material is directionally induced to be consistent, so that the cracking in the long-cycle process is obviously lightened. The acid phosphate coating layer is introduced to the surface of the high-nickel ternary layered oxide material, so that the contact between the high-nickel ternary layered oxide material and sulfide electrolyte is avoided, side reactions can be effectively inhibited, meanwhile, alkaline impurities on the surface of the quaternary positive electrode material can be effectively consumed by the acid phosphate, and the conductivity of the surface layer of the quaternary positive electrode material is improved.
Drawings
Fig. 1 is an SEM of NCMA quaternary positive electrode material prepared in example 1 (a. Positive electrode material surface morphology; b. Positive electrode material cross-sectional morphology).
Fig. 2 is an SEM of NCMA quaternary positive electrode material prepared in comparative example 1 (a. Positive electrode material surface morphology; b. Positive electrode material cross-sectional morphology).
Detailed Description
The preparation method of NCMA quaternary positive electrode material of the invention comprises the following steps:
step 1, preparing NCMA precursor by adopting a coprecipitation method;
Step 2, preparing a radial NCMA quaternary positive electrode material by adopting solid phase one-time roasting;
and 3, carrying out acid phosphate adhesion and secondary roasting on the prepared radial NCMA quaternary positive electrode material to obtain the radial NCMA quaternary positive electrode material after acid phosphate adhesion.
The chemical formula of the NCMA quaternary positive electrode material is LiNi wCoxMnyAlzO2, wherein w is more than or equal to 0.88 and less than or equal to 0.95,0.03, x is more than or equal to 0.06,0.01 and less than or equal to y is more than or equal to 0.03,0.01 and less than or equal to z is more than or equal to 0.03, and w+x+y+z=1.
The mass ratio of NCMA quaternary positive electrode material to acid phosphate is 0.001-0.05:1, and the acid phosphate is Zr (HPO 4)2·H2 O).
The thickness of the coating layer of the radial NCMA quaternary positive electrode material is 10-50 nm.
In the step 3, the temperature of the second roasting is 400-600 ℃, the time of the second roasting is 5-10 h, and the second roasting is performed in an oxygen atmosphere.
The preparation method comprises the steps of mixing NCMA precursor, liOH and a directional growth inducer to obtain a mixture, roasting the mixture for the first time to obtain a material after primary roasting, cooling and crushing the material after primary roasting to obtain a radial NCMA quaternary positive electrode material with the particle size of 6-20 mu m, wherein the molar ratio of NCMA precursor to LiOH to the directional growth inducer is 1:1-1.06:0.001-0.01.
The directional growth inducer is WO 3.
The mixing is dry mixing, the temperature of the first roasting is 700-850 ℃, the time of the first roasting is 10-20 h, and the first roasting is performed in an oxygen atmosphere.
NCMA quaternary positive electrode materials prepared by the preparation method.
An all-solid-state battery employing the NCMA quaternary positive electrode material described above.
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Those skilled in the art will readily recognize various non-critical parameters that may be varied or altered to produce substantially the same results.
Example 1
A preparation method of NCMA quaternary positive electrode material comprises the following steps:
NCMA precursor (molar ratio: ni: co: mn: al=88:6:3:3), liOH and directional growth inducer WO 3 are directly stirred and mixed in a powder high-speed mixer according to the molar ratio of 1:1.05:0.003 to obtain a mixture, the mixture is baked for 15 hours in the oxygen atmosphere of 765 ℃ of a roller kiln, and then is cooled, crushed and screened to obtain a radial NCMA quaternary positive electrode material with the particle size of 12.5 mu m, wherein the chemical formula of the NCMA quaternary positive electrode material is LiNi 0.88Co0.06Mn0.03Al0.03O2. Since the content of W element is extremely small, it is not represented in the chemical formula.
The radial NCMA quaternary positive electrode material and Zr (HPO 4)2·H2 O) are subjected to fluidized bed coating according to the mass ratio of 1:0.005, so that Zr (HPO 4)2·H2 O) is uniformly attached to the surface of the NCMA quaternary positive electrode material to obtain an attached material, the attached material is baked for 8 hours in an oxygen atmosphere at 500 ℃, and then the NCMA quaternary positive electrode material is obtained by cooling, crushing, sieving and demagnetizing, wherein the thickness of the coating layer of the NCMA quaternary positive electrode material is 31nm.
Example 2
In comparison with example 1, NCMA quaternary positive electrode material and Zr (HPO 4)2·H2 O were dry mixed in a mass ratio of 1:0.001, the remaining conditions being unchanged.
A preparation method of NCMA quaternary positive electrode material comprises the following steps:
NCMA precursor (molar ratio: ni: co: mn: al=88:6:3:3), liOH and directional growth inducer WO 3 are directly stirred and mixed in a powder high-speed mixer according to the molar ratio of 1:1.05:0.003 to obtain a mixture, the mixture is baked for 15 hours in the oxygen atmosphere of 765 ℃ of a roller kiln, and then is cooled, crushed and screened to obtain a radial NCMA quaternary positive electrode material with the particle size of 12.3 mu m, wherein the chemical formula of the NCMA quaternary positive electrode material is LiNi 0.88Co0.06Mn0.03Al0.03O2. Since the content of W element is extremely small, it is not represented in the chemical formula.
The radial NCMA quaternary positive electrode material and Zr (HPO 4)2·H2 O) are subjected to fluidized bed coating according to the mass ratio of 1:0.002, so that Zr (HPO 4)2·H2 O) is uniformly attached to the surface of the NCMA quaternary positive electrode material to obtain an attached material, the attached material is baked for 8 hours in an oxygen atmosphere at 500 ℃, and then the NCMA quaternary positive electrode material is obtained by cooling, crushing, sieving and demagnetizing, wherein the thickness of the coating layer of the NCMA quaternary positive electrode material is 15nm.
Example 3
In comparison with example 1, NCMA quaternary positive electrode material was designed as LiNi in composition 0.90Co0.05Mn0.03Al0.02O2
A preparation method of NCMA quaternary positive electrode material comprises the following steps:
NCMA precursor (molar ratio: ni: co: mn: al=90:5:3:2) and LiOH, directional growth inducer WO 3 are directly stirred and mixed in a powder high-speed mixer according to the molar ratio of 1:1.05:0.003 to obtain a mixture, the mixture is baked for 15 hours in the oxygen atmosphere of 765 ℃ of a roller kiln, and then cooled, crushed and screened to obtain the NCMA quaternary positive electrode material with the particle size of 12.7 mu m, wherein the chemical formula of the NCMA quaternary positive electrode material is LiNi 0.90Co0.05Mn0.03Al0.02O2.
The radial NCMA quaternary positive electrode material and Zr (HPO 4)2·H2 O) are subjected to fluidized bed coating according to the mass ratio of 1:0.005, so that Zr (HPO 4)2·H2 O) is uniformly attached to the surface of the NCMA quaternary positive electrode material to obtain an attached material, the attached material is baked for 8 hours in an oxygen atmosphere at 500 ℃, and then the NCMA quaternary positive electrode material is obtained by cooling, crushing, sieving and demagnetizing, wherein the thickness of the coating layer of the NCMA quaternary positive electrode material is 30nm.
Example 4
In comparison with example 1, the doping amount ratio of the directional growth inducer was designed to be 1:0.005, and the remaining conditions were unchanged.
The preparation method of the novel quaternary positive electrode material for the all-solid-state battery comprises the following steps:
NCMA precursor (molar ratio: ni: co: mn: al=88:6:3:3), liOH and directional growth inducer WO 3 are directly stirred and mixed in a powder high-speed mixer according to the molar ratio of 1:1.05:0.005 to obtain a mixture, the mixture is baked for 15 hours in the oxygen atmosphere of 765 ℃ of a roller kiln, and then is cooled, crushed and screened to obtain a radial NCMA quaternary positive electrode material with the particle size of 12.3 mu m, wherein the chemical formula of the NCMA quaternary positive electrode material is LiNi 0.88Co0.06Mn0.03Al0.03O2. Since the content of W element is extremely small, it is not represented in the chemical formula.
The radial NCMA quaternary positive electrode material and Zr (HPO 4)2·H2 O) are subjected to fluidized bed coating according to the mass ratio of 1:0.005, so that Zr (HPO 4)2·H2 O) is uniformly attached to the surface of the NCMA quaternary positive electrode material to obtain an attached material, the attached material is baked for 8 hours in an oxygen atmosphere at 500 ℃, and then the NCMA quaternary positive electrode material is obtained by cooling, crushing, sieving and demagnetizing, wherein the thickness of the coating layer of the NCMA quaternary positive electrode material is 30nm.
Comparative example 1
NCMA precursor (molar ratio: ni: co: mn: al=88:6:3:3) and LiOH are directly stirred and mixed in a powder high-speed mixer according to a molar ratio of 1:1.05 to obtain a mixture, the mixture is baked for 15 hours in a roller kiln at 765 ℃ under oxygen atmosphere, and then is cooled, crushed and screened to obtain a NCMA quaternary positive electrode material with unordered stacking and a grain diameter of 12.5 mu m, wherein the chemical formula of the NCMA quaternary positive electrode material is LiNi 0.88Co0.06Mn0.03Al0.03O2.
And (3) manufacturing an all-solid-state battery, namely respectively grinding and uniformly mixing NCMA quaternary positive electrode materials manufactured in the examples 1-4 and the comparative example 1 and the Li 10GeP2S12 sulfide electrolyte according to the mass ratio of 7:3, so as to prepare the composite positive electrode powder. 100g of Li 10GeP2S12 sulfide electrolyte was weighed into a solid-state battery mold and molded under 10 MPa. The negative electrode adopts Li-In alloy. When the battery is assembled, 10mg of composite positive electrode powder is weighed, the battery is assembled according to the sequence of the composite stainless steel sheet, the negative electrode, the electrolyte, the composite positive electrode and the stainless steel sheet, the battery is extruded and molded under the pressure of 15MPa, and finally the battery is fastened by using screws. The assembly process was performed in an argon filled glove box. The electrical performance test was also performed in a glove box, using a new-wire battery test system at 35 ℃ with a test voltage range of 2.1-3.68 v, and the first discharge capacity, efficiency and 100-week capacity retention were tested, and the test results are shown in table 1.
Table 1 electrical performance test data
As can be seen from the data in Table 1, compared with comparative example 1, the capacity and cycle of NCMA quaternary positive electrode materials in examples 1-5 are better, mainly because Zr (HPO 4)2·H2 O is coated and then chemical reaction is carried out to eliminate residual lithium, so that the conductivity of the interface between NCMA quaternary positive electrode materials and sulfide electrolyte is improved, on the other hand, the coating layer effectively prevents side reaction caused by direct contact between high-nickel layered oxide and sulfide, thereby improving the specific capacity of materials, and meanwhile, the radial structure effectively prevents internal cracking of the positive electrode materials, inhibits contact failure and improves the cycle performance of materials.
The invention eliminates the characteristic of residual lithium by chemical reaction after coating by using Zr (HPO 4) 2.H2O, improves the ion transmission property of the surface of the material, and effectively improves the electrochemical performance of the material. According to the characteristic that Zr (HPO 4) 2.H2O can generate a stable and uniform coating layer on the surface layer of the material, a fluidized bed coating and a high-temperature solid phase method are used for generating the coating layer, so that the problem of poor interfacial compatibility between NCMA and sulfide electrolyte is solved. Zr (HPO 4) 2.H2O is used as a coating layer, two elements of Zr and P can be simultaneously introduced, and the materials are uniformly dispersed in the preparation process, so that the preparation method is low in cost, can be used for batch preparation, and is suitable for industrial production.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1.一种NCMA四元正极材料的制备方法，其特征在于，包括以下步骤：1. A method for preparing an NCMA quaternary cathode material, characterized by comprising the following steps: 步骤1，采用共沉淀法制备NCMA前驱体；Step 1: Prepare NCMA precursor using co-precipitation method; 步骤2，采用固相一次焙烧制备放射状NCMA四元正极材料；Step 2: Radial NCMA quaternary cathode material is prepared by solid-phase one-time calcination; 步骤3，对制备的放射状NCMA四元正极材料进行酸式磷酸盐附着和二次焙烧，得到酸式磷酸盐附着后的放射状NCMA四元正极材料；Step 3: The prepared radial NCMA quaternary cathode material is subjected to acid phosphate attachment and secondary calcination to obtain the radial NCMA quaternary cathode material after acid phosphate attachment. 所述酸式磷酸盐为Zr(HPO4)2·H2O；The acidic phosphate is Zr( HPO4 ) 2 · H2O ; 所述步骤2具体为：将NCMA前驱体与LiOH和定向生长诱导剂进行混合，得到混合物；将混合物进行第一次焙烧，得到一次焙烧后材料；一次焙烧材料进行冷却、粉碎后，得到粒径为6～20μm的放射状NCMA四元正极材料； NCMA前驱体、LiOH及定向生长诱导剂的摩尔比为1: 1～1.06 : 0.001～0.01。Step 2 specifically involves: mixing the NCMA precursor with LiOH and a directional growth inducer to obtain a mixture; subjecting the mixture to a first calcination to obtain a material after one calcination; cooling and pulverizing the first calcined material to obtain a radial NCMA quaternary cathode material with a particle size of 6–20 μm; the molar ratio of the NCMA precursor, LiOH, and directional growth inducer is 1: 1–1.06: 0.001–0.01. 2.根据权利要求1所述NCMA四元正极材料的制备方法，其特征在于，所述NCMA四元正极材料的化学式为LiNiwCoxMnyAlzO2，其中，0.88≤w≤0.95，0.03≤x≤0.06，0.01≤y≤0.03，0.01≤z≤0.03，且w+x+y+z＝1。2. The method for preparing the NCMA quaternary cathode material according to claim 1, characterized in that the chemical formula of the NCMA quaternary cathode material is LiNi w Co x Mn y Al z O 2 , wherein 0.88≤w≤0.95, 0.03≤x≤0.06, 0.01≤y≤0.03, 0.01≤z≤0.03, and w+x+y+z＝1. 3.根据权利要求1所述NCMA四元正极材料的制备方法，其特征在于，所述NCMA四元正极材料、酸式磷酸盐的质量比为0.001～0.05 : 1。3. The method for preparing the NCMA quaternary cathode material according to claim 1, wherein the mass ratio of the NCMA quaternary cathode material to the acid phosphate is 0.001 to 0.05:1. 4.根据权利要求1所述NCMA四元正极材料的制备方法，其特征在于，所述放射状NCMA四元正极材料的包覆层的厚度为10～50nm。4. The method for preparing NCMA quaternary cathode material according to claim 1, wherein the thickness of the coating layer of the radial NCMA quaternary cathode material is 10-50 nm. 5.根据权利要求1所述NCMA四元正极材料的制备方法，其特征在于，所述步骤3中，第二次焙烧的温度为400～600℃，第二次焙烧的时间为5～10h，第二次焙烧在氧气的气氛中进行。5. The method for preparing NCMA quaternary cathode material according to claim 1, characterized in that, in step 3, the temperature of the second calcination is 400-600℃, the time of the second calcination is 5-10h, and the second calcination is carried out in an oxygen atmosphere. 6.根据权利要求1所述NCMA四元正极材料的制备方法，其特征在于，所述定向生长诱导剂为WO3。6. The method for preparing the NCMA quaternary cathode material according to claim 1, wherein the directional growth inducing agent is WO3 . 7.根据权利要求1所述NCMA四元正极材料的制备方法，其特征在于，所述混合为干法混合，第一次焙烧的温度为700～850℃，第一次焙烧的时间为10～20h，第一次焙烧在氧气的气氛中进行。7. The method for preparing NCMA quaternary cathode material according to claim 1, characterized in that the mixing is a dry mixing, the temperature of the first calcination is 700-850°C, the time of the first calcination is 10-20 h, and the first calcination is carried out in an oxygen atmosphere. 8.如权利要求1-7任一项所述的制备方法制得的NCMA四元正极材料。8. The NCMA quaternary cathode material prepared by the preparation method according to any one of claims 1-7. 9.一种全固态电池，其特征在于，采用权利要求8中的NCMA四元正极材料。9. An all-solid-state battery, characterized in that it uses the NCMA quaternary cathode material as described in claim 8.
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CN111987309A (en) * 2020-08-12 2020-11-24 中南大学 A kind of lithium titanium scandium phosphate modified lithium ion battery cathode material and preparation method thereof

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CN107221645A (en) * 2017-07-06 2017-09-29 广州朝锂新能源科技有限公司 Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof
CN111987309A (en) * 2020-08-12 2020-11-24 中南大学 A kind of lithium titanium scandium phosphate modified lithium ion battery cathode material and preparation method thereof

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