CN115579450A - Method for improving sintering quality of lithium battery positive electrode material by insulating refractory material - Google Patents

Method for improving sintering quality of lithium battery positive electrode material by insulating refractory material Download PDF

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Publication number
CN115579450A
CN115579450A CN202211368339.8A CN202211368339A CN115579450A CN 115579450 A CN115579450 A CN 115579450A CN 202211368339 A CN202211368339 A CN 202211368339A CN 115579450 A CN115579450 A CN 115579450A
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kiln
sintering
insulating
refractory
lithium battery
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Inventor
祁雅琼
张秀荣
张呈祥
刘文静
闫雅倩
张光睿
郝先库
李璐
阚丽欣
彭维
谌礼兵
王计平
曹建伟
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Baotou Ande Kiln Technology Co ltd
China Northern Rare Earth Group High Tech Co ltd
Tianjin Baogang Rare Earth Research Institute Co Ltd
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Baotou Ande Kiln Technology Co ltd
China Northern Rare Earth Group High Tech Co ltd
Tianjin Baogang Rare Earth Research Institute Co Ltd
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Priority to CN202211368339.8A priority Critical patent/CN115579450A/en
Publication of CN115579450A publication Critical patent/CN115579450A/en
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/12—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity with special arrangements for preheating or cooling the charge
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/12—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity with special arrangements for preheating or cooling the charge
    • F27B2009/122—Preheating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/12—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity with special arrangements for preheating or cooling the charge
    • F27B2009/124—Cooling
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Abstract

The invention provides a method for improving the sintering quality of a lithium battery anode material by using an insulating refractory material, wherein the insulating material is formed by cerium-doped lanthanum zirconate solid solution and a high-temperature adhesive, and the insulating material is sprayed on the surfaces of a kiln wall and a kiln top refractory material of a sintering kiln to obtain the sintering kiln with the insulating refractory material; compared with a conventional sintering kiln, the sintering kiln for isolating the refractory material isolates the pollution of metal ions in the refractory material to the anode material, and also isolates the corrosion and erosion of the alkaline compound of the anode material to the refractory material, the qualified rate of the sintered anode material product is improved by more than 10%, the energy is saved by more than 15% per ton of the anode material, and the service life of the sintering kiln is prolonged by more than 1 time. The insulating material is applied to the lithium battery anode material sintering kiln, and the bottleneck problem puzzling the anode material sintering is solved.

Description

Method for improving sintering quality of lithium battery positive electrode material by insulating refractory material
Technical Field
The invention relates to the field of lithium batteries, in particular to a method for improving the sintering quality of a lithium battery anode material by using an insulating refractory material.
Background
In 1987, akira Yoshino adopted LiCoO 2 As a positive electrode, a graphite material as a negative electrode developed the earliest lithium ion secondary battery model, which was finally adopted by Sony corporation, and introduced the first commercial lithium ion battery worldwide in 1991, and in 1996 and 1997, japan and the United states followed by the United statesLiFePO of olivine structure was developed 4 Anode material, liFePO 4 Compared with other positive-price materials, the lithium secondary battery has the advantages of easily available raw materials, low price and no pollution, and immediately causes extensive research and attention in the world because the lithium secondary battery solves the problem of safety performance of the lithium battery, simultaneously reduces the preparation cost, the working voltage of the battery exceeds 3.5V, and the specific energy reaches 120 Wh/kg. Through the technological improvement and progress of over twenty years, the lithium ion battery becomes the first choice of chemical power supply and is widely applied to the fields of energy storage and power systems.
At present, the application field of lithium batteries is gradually expanded, the demand is continuously increased, the performance of a cathode material is an important factor for limiting the capacity of the lithium battery, and the commonly used cathode material of the lithium battery mainly comprises olivine type LiFePO 4 Layered LiCoO 2 Spinel type LiMn 2 O 4 And the ternary material LiNi 1-x-y Co x M y O 2 (M = Mn, al), and the like. The working principle of the lithium battery is that lithium ions are extracted from a positive electrode material crystal lattice during charging and inserted into a negative electrode material crystal lattice through an electrolyte, and the lithium ions are extracted from the negative electrode material crystal lattice during discharging and inserted into the positive electrode material crystal lattice through the electrolyte. The lithium ion battery anode material is prepared by a solid phase method or a precipitation method through high-temperature sintering, and a high-temperature sintering kiln is crucial to the quality of the anode material. The commonly used sintering kiln mainly comprises a push plate furnace, a roller bed furnace and a rotary furnace, and the working temperature is between room temperature and 1050 ℃. The sintering of the anode material in the lithium battery is carried out by saggars, stacked and sintered at present, and mainly performed by roller kilns and push plate kilns.
The lithium battery anode material has complex chemical reaction in the high-temperature sintering process, and particularly has the problems of temperature stability in a sintering kiln, pollution of refractory metal ions to the anode material, corrosion or erosion of the refractory material of the kiln body by gas released in the reaction process of the anode material and alkaline lithium oxide in the industrial production process, and the like, and the bottleneck problems are that the anode material product with stable performance is difficult to provide in the industrial production. In the production process, the uniformity of the temperature field in the kiln is difficult to reach an ideal state, so that the anode material cannot meet the requirement of a high-end lithium battery, such as at high temperatureThe anode material is subjected to free water, crystallization water and gas discharge, decomposition, synthesis and crystal forming are also required to be completed, the temperature difference of the inner section of the kiln is overlarge in a high-temperature area, the anode material is over-burnt at a higher temperature or close to the edge of a sagger, the particle size of the material is agglomerated, the anode material is incompletely reacted at a lower temperature or in the middle of the sagger, the consistency of products is difficult to ensure in industrial production, and the uniformity of a temperature field in the kiln has important influence on the final performance of the anode material; the refractory material erosion of the kiln is caused by the complicated physical and chemical reaction of the anode material at high temperature, li 2 CO 3 And Li 2 O and SiO in refractory material 2 And Al 2 O 3 The compounds react to form low-melting eutectic lithium silicate, lithium aluminate and other compounds to cause corrosion; at high temperature, the refractory material releases some metal ions, the metal ions are suspended in hot gas in the kiln, some metal ions react when encountering the anode material, in addition, the anode material enters a cooling section, part of the metal ions suspended in the hot gas fall onto the surface of the anode material in the sagger, such as metal impurities of chromium, copper, iron, zinc and the like, when the voltage of the battery reaches the oxidation-reduction potential of the metal elements, the metal is oxidized at the anode and then reduced at the cathode, the metal deposited at the cathode easily damages a diaphragm, the self-discharge of the battery is caused, and meanwhile, the anode material also hardly reaches the required performance indexes of specific capacity, conductivity and the like. The bottleneck of hindering the industrialized high-temperature sintering of the lithium battery anode material at present is to solve the problems of uniformity of a temperature field in a kiln, energy conservation, consumption reduction, erosion and corrosion of refractory materials and pollution to the anode material.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for improving the sintering quality of a lithium battery anode material by insulating a refractory material, which solves the bottleneck problems of temperature field uniformity, erosion and corrosion of the refractory material and pollution to the anode material in a high temperature sintering kiln for lithium battery anode material industrialization, improves the performance indexes of the anode material, such as specific capacity, conductivity, and the like, and realizes energy saving, consumption reduction and extension of the service life of the sintering kiln.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for improving the sintering quality of a lithium battery anode material by using an insulating refractory material comprises the following steps:
(1) Preparation of insulation materials
Lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed according to La 2 (Zr 1-x Ce x ) 2 O 7 Mixing uniformly according to the stoichiometric ratio, wherein x =0.2-0.8, forming cerium-doped lanthanum zirconate solid solution powder at the firing temperature of 1400-1500 ℃, adding the powder into a mixed solution of water and a dispersing agent, wherein the mass ratio of the powder to the water is (1.2-2): 1, the adding amount of the dispersing agent is 3 per mill-1% of the powder, and grinding the slurry to D particle size through grinding (90) Less than or equal to 10.0 mu m, and then uniformly mixing the serous fluid and the high-temperature adhesive according to the proportion of 1 (0.8-1.5) to obtain an insulating material;
(2) Isolated sintering kiln refractory material
Spraying a layer of insulating material on the surface of the refractory material, wherein the spraying thickness is 0.2-0.4mm, drying at room temperature, heating according to the drying program of a sintering kiln, keeping the temperature for 4 hours when the highest temperature reaches 1250 ℃, and firmly combining the insulating material and the refractory material together to obtain the sintering kiln with the insulating refractory material;
(3) Sintering of positive electrode material
And (3) putting the sagger filled with the lithium battery anode raw material into a sintering kiln for isolating refractory materials, and passing through a preheating zone, a high-temperature zone and a cooling zone to obtain anode material powder.
Further, the dispersant is one or a mixture of more than two of BYK190, RT-8040 and RT-8022.
Further, the high-temperature binder is Al (H) 2 PO 4 ) 3 。
Further, in the step (2), before the insulating material is sprayed, refractory clay and dust are removed from the surfaces of the refractory materials on the kiln wall and the kiln top of the sintering kiln.
Further, in the step (3), the temperature of a high-temperature zone of the sintering kiln for isolating the refractory material is controlled to be 800-850 ℃.
Further, in the step (2), the sintering kiln is a pusher kiln or a roller kiln.
Further, in the step (3), the lithium battery positive electrode raw material comprises LiCoO 2 、LiMn 2 O 4 、 LiFePO 4 And LiNi 1-x- y Co x M y O 2 Wherein M = Mn, al.
The core of the method of the invention is: 1) Ce 4+ La doping 2 Zr 2 O 7 Structure of solid solution with Ce in solid solution 4+ And Zr 4+ Change in the mass ratio, zr 4+ When the ratio is low, zr 4+ Into CeO 2 In crystal lattice, cause CeO 2 The lattice distortion and defects enhance the mobility of lattice oxygen vacancies and form a cubic fluorite structured lanthanum cerium zirconium solid solution; with Zr 4+ The ratio gradually increases as CeO 2 The content of the predominant cubic phase is reduced, and ZrO 2 The content of the main tetragonal phase is increased; ce 4+ Into ZrO 2 Cerium lanthanum zirconate solid solution, ce, forming tetragonal phase in lattice 4+ Into ZrO 2 The crystal lattice is beneficial to the formation of a tetragonal phase cerium lanthanum zirconate solid solution with good thermal stability, lanthanum in the solid solution inhibits the high-temperature sintering of powder, and the cerium lanthanum zirconate solid solution improves the high-temperature thermal stability of the insulating material, so that the infrared radiance of the insulating material is improved, and the heat conductivity coefficient of the insulating material is reduced; 2) The insulating material is tightly combined with the refractory material to form a layer of glaze, so that the pollution of metal ions released by the refractory material to the anode material is isolated, the corrosion of corrosive gas and alkaline compounds generated by the reaction of the anode material to the refractory material is isolated, and the glaze also has the functions of corrosion resistance, wear resistance, thermal barrier and the like; 3) The radiation function of the insulating material obviously enhances the radiation heat transfer of the sintering kiln, improves the uniformity of the temperature field in the kiln, and the heat transferred from the insulating material to the anode material according to the Stefan-Boltzmann law is in direct proportion to the fourth power of the absolute temperature of the insulating material, and the spraying of the insulating material obviously enhances the heating energy of the anode material; 4) The insulating material changes the wave spectrum distribution of infrared radiation in the kiln, converts discontinuous wave spectrum into continuous wave spectrum, the emitted far infrared ray directly penetrates into the anode material to make the molecule in the material vibrate and generate energy level transition,and infrared rays with a certain wave band are radiated, so that heat is generated, the materials are heated from inside to outside, the reaction time of the materials is shortened, and the uniformity of components in the materials is improved due to uniform heating.
Compared with the prior art, the method for improving the sintering quality of the lithium battery anode material by using the insulating refractory material has the following advantages:
(1) The invention adopts cerium-doped lanthanum zirconate solid solution and high-temperature adhesive to form the insulating material, has excellent stability in the environments of high temperature, reduction, oxidation and alkaline compounds, obviously enhances the corrosion resistance and the erosion resistance of the sintering kiln, prolongs the service life of the sintering kiln and solves the difficult problem of the sintering kiln.
(2) The material is tightly combined with the refractory material, and a layer of glaze is formed on the surface of the refractory material, so that corrosive gas and alkaline compounds generated in the reaction process of the anode material are well isolated from the refractory material, the corrosion and erosion to the refractory material are avoided, the wear resistance of the inner wall is enhanced, and the pollution of metal ions in the refractory material to the anode material is shielded.
(3) La of the invention 2 (Zr 1-x Ce x ) 2 O 7 The thermal barrier material has a thermal expansion coefficient matched with a refractory material, and has a low heat conductivity coefficient, a thermal insulation function, a temperature reduction effect on the outer wall of the sintering kiln, and an effective energy consumption reduction effect.
(4) La of the invention 2 (Zr 1-x Ce x ) 2 O 7 The high-emissivity anode material has high infrared radiation emissivity, improves the uniformity of a temperature field in a sintering kiln, promotes the uniform reaction of the anode material, and realizes the homogenization and complete reaction of the components of the anode material.
(5) The far infrared rays emitted by the insulating material can penetrate through incompletely combusted particles in the smoke dust, heat the interior of the smoke dust and realize complete combustion, so that the content of unburned dust in the smoke dust is reduced.
(6) The far infrared rays emitted by the insulating material directly penetrate into the anode material for heating reaction, so that the reaction time of the anode material is obviously shortened, and compared with a conventional sintering kiln with the same model, the production capacity is obviously improved.
(7) The invention is easy to realize the spraying of the insulating material in both a newly-built sintering kiln and the existing sintering kiln.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail with reference to examples.
Example 1
A method for improving the sintering quality of a lithium battery anode material by using an insulating refractory material comprises the following steps:
(1) Preparing an insulating material: lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed homogeneously in stoichiometric ratio and La is formed at burning temperature 1500 deg.c 2 (Zr 0.8 Ce 0.2 ) 2 O 7 Powder, 200 parts of powder is added to 100 parts of water and 1.1 parts of dispersant mixed solution, and slurry is ground to D particle size by grinding (90) After 10.0 μm the slurry was transferred to a dispersion tank and 300 parts of Al (H) were slowly added 2 PO 4 ) 3 Uniformly mixing the solution to obtain an isolation material;
(2) Isolating refractory materials of a pushed slab kiln: removing refractory mud and dust from the surfaces of refractory materials of a kiln wall and a kiln top of the pushed slab kiln, spraying a layer of insulating material on the surface of the refractory materials, wherein the spraying thickness is 0.3mm, drying at room temperature, heating according to a drying program of the pushed slab kiln, keeping the temperature for 4 hours when the highest temperature reaches 1250 ℃, and firmly combining the insulating material and the refractory materials together to obtain the pushed slab kiln with the insulating refractory materials;
(3) Sintering of the anode material: the temperature of a high-temperature area of the pushed slab kiln for isolating refractory materials is controlled to be 850 ℃, and LiCoO is filled in the pushed slab kiln 2 The sagger of the raw material enters a pushed slab kiln isolated from refractory materials and passes through a preheating zone, a high-temperature zone and a cooling zone to obtain layered LiCoO 2 A positive electrode material;
(4) And (3) performance comparison analysis: compared with the conventional pushed slab kiln, the pushed slab kiln for isolating the refractory material isolates the refractory materialMetal ion pair LiCoO 2 While also sequestering LiCoO 2 Corrosion and erosion of refractory materials by moderately basic compounds, sintering of LiCoO 2 The product percent of pass is improved by 10.5 percent, and each ton of LiCoO 2 The energy is saved by 15.6 percent, and the service life of the pushed slab kiln is prolonged by 1.5 times.
Example 2
A method for improving the sintering quality of a lithium battery anode material by using an insulating refractory material comprises the following steps:
(1) Preparing an insulating material: lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed homogeneously in stoichiometric ratio and La is formed at burning temperature 1500 deg.c 2 (Zr 0.6 Ce 0.4 ) 2 O 7 Powder, 200 parts of powder is added to 100 parts of water and 1.1 parts of dispersant mixed solution, and slurry is ground to D particle size by grinding (90) After 10.0 μm the slurry was transferred to a dispersion tank and 300 parts of Al (H) were slowly added 2 PO 4 ) 3 Uniformly mixing the solution to obtain an isolation material;
(2) Isolating refractory materials of the roller kiln: removing refractory mortar and dust from the surfaces of refractory materials on the kiln wall and the kiln top of the roller kiln, spraying a layer of insulating material on the surface of the refractory materials, wherein the spraying thickness is 0.3mm, drying at room temperature, heating according to a drying program of the roller kiln, keeping the temperature for 4 hours when the highest temperature reaches 1250 ℃, and firmly combining the insulating material and the refractory materials together to obtain the roller kiln with the insulating refractory materials;
(3) Sintering of the anode material: controlling the temperature of a high-temperature area of the roller kiln for isolating refractory materials to be 840 ℃, and filling LiMn in the high-temperature area 2 O 4 The sagger of the raw material enters a roller kiln isolated from refractory materials, and the spinel LiMn is obtained through a preheating zone, a high-temperature zone and a cooling zone 2 O 4 A positive electrode material;
(4) Performance comparison analysis: compared with the conventional roller kiln, the roller kiln for isolating the refractory material isolates the metal ion pair LiMn in the refractory material 2 O 4 While isolating the LiMn 2 O 4 Corrosion and erosion of refractory materials by medium-basic compounds, sintered LiMn 2 O 4 The product percent of pass is improved by 15.6 percent, and each ton of LiMn 2 O 4 The energy is saved by 16.1 percent, and the service life of the roller kiln is prolonged by 1.8 times.
Example 3
A method for improving the sintering quality of a lithium battery anode material by using an insulating refractory material comprises the following steps:
(1) Preparing an insulating material: lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed homogeneously in stoichiometric ratio to form La at 1400 deg.c 2 (Zr 0.4 Ce 0.6 ) 2 O 7 Powder, 200 parts of powder is added to 130 parts of water and 1 part of dispersant mixed solution, and slurry is ground to D particle size by grinding (90) After 10.0 μm the slurry was transferred to a dispersion tank and 330 parts of Al (H) were slowly added 2 PO 4 ) 3 Uniformly mixing the solution to obtain an insulating material;
(2) Isolating refractory materials of the pushed slab kiln: removing refractory mortar and dust from the surfaces of refractory materials of the kiln wall and the kiln top of the pushed slab kiln, spraying a layer of insulating material on the surface of the refractory materials, wherein the spraying thickness is 0.3mm, drying at room temperature, heating according to a drying program of the pushed slab kiln, keeping the temperature for 4 hours when the highest temperature reaches 1250 ℃, and firmly combining the insulating material and the refractory materials to obtain the pushed slab kiln with the insulating refractory materials;
(3) Sintering of the anode material: the temperature of a high-temperature area of the pushed slab kiln for isolating refractory materials is controlled at 800 ℃, and LiFePO is filled in the pushed slab kiln 4 The sagger of the raw material enters a pushed slab kiln isolated from refractory materials, and the olivine type LiFePO is obtained through a preheating zone, a high-temperature zone and a cooling zone 4 A positive electrode material;
(4) And (3) performance comparison analysis: compared with the conventional pushed slab kiln, the pushed slab kiln for isolating the refractory material isolates the metal ions in the refractory material from LiFePO 4 While isolating LiFePO 4 Corrosion and erosion of refractory material by medium-alkaline compounds, sintering LiFePO 4 The product percent of pass is improved by 16.7 percent, and each ton of LiFePO 4 The energy is saved by 17.2 percent, and the service life of the pushed slab kiln is prolonged by 2.0 times.
Example 4
A method for improving the sintering quality of a lithium battery anode material by using an insulating refractory material comprises the following steps:
(1) Preparing an insulating material: lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed homogeneously in stoichiometric ratio to form La at the burning temperature of 1400 deg.c 2 (Zr 0.2 Ce 0.8 ) 2 O 7 Powder, 200 parts of powder is added to 130 parts of water and 1 part of dispersant mixed solution, and slurry is ground to D particle size by grinding (90) After 10.0 μm the slurry was transferred to a dispersion tank and 330 parts of Al (H) were slowly added 2 PO 4 ) 3 Uniformly mixing the solution to obtain an insulating material;
(2) Isolating refractory materials of the roller kiln: removing refractory mud and dust from the surfaces of refractory materials of a kiln wall and a kiln top of the roller kiln, spraying a layer of insulating material on the surface of the refractory materials, wherein the spraying thickness is 0.3mm, drying at room temperature, heating according to a drying program of the roller kiln, keeping the temperature for 4 hours when the highest temperature reaches 1250 ℃, and firmly combining the insulating material and the refractory materials together to obtain the roller kiln with the insulating refractory materials;
(3) Sintering of the positive electrode material: the temperature of the high-temperature area of the roller kiln for isolating refractory materials is controlled at 850 ℃, and LiNi is filled in the roller kiln 1-x-y Co x M y O 2 The sagger of (M = Mn, al) raw material enters a roller kiln for isolating refractory materials, and a ternary material LiNi is obtained through a preheating zone, a high-temperature zone and a cooling zone 1-x-y Co x M y O 2 A positive electrode material;
(4) Performance comparison analysis: compared with the conventional roller kiln, the roller kiln for isolating the refractory material isolates the metal ion pairs LiNi in the refractory material 1-x-y Co x M y O 2 While isolating LiNi 1-x-y Co x M y O 2 Corrosion and erosion of refractory materials by moderately basic compounds, sintering of LiNi 1-x-y Co x M y O 2 The product percent of pass is improved by 20.6 percent, and each ton of LiNi 1-x-y Co x M y O 2 The energy is saved by 18.5 percent, and the service life of the roller kiln is prolonged by 2.2 times.
Comparative example 1
(1) Preparing an insulating material: lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed homogeneously in stoichiometric ratio to form La at the burning temperature of 1200 deg.c 2 (Zr 0.8 Ce 0.2 ) 2 O 7 Powder, 200 parts of the powder is added into 100 parts of water and 1.1 parts of dispersant mixed solution, and the slurry is ground to D particle size by grinding (90) After 10.0 μm the slurry was transferred to a dispersion tank and 300 parts of Al (H) were slowly added 2 PO 4 ) 3 Uniformly mixing the solution to obtain an isolation material;
(2) Performance comparison analysis: compared with the conventional pushed slab kiln, the pushed slab kiln for isolating the refractory material isolates the metal ions in the refractory material from LiCoO 2 While also sequestering LiCoO 2 Corrosion and erosion of refractory materials by medium-basic compounds, sintering of LiCoO 2 The product percent of pass is improved by 7.2 percent, and each ton of LiCoO 2 The energy is saved by 9.8 percent, and the service life of the pushed slab kiln is prolonged by 0.4 time.
Comparative example 2
(1) Preparing an insulating material: lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed homogeneously in stoichiometric ratio and La is formed at burning temperature 1500 deg.c 2 (Zr 0.6 Ce 0.4 ) 2 O 7 Powder, 200 parts of powder is added to 100 parts of water and 1.1 parts of dispersant mixed solution, and slurry is ground to D particle size by grinding (90) After 10.0 μm, the slurry was transferred to a dispersion tank, and 200 parts of Al (H) was slowly added 2 PO 4 ) 3 Uniformly mixing the solution to obtain an insulating material;
(2) And (3) performance comparison analysis: compared with the conventional roller kiln, the roller kiln for isolating the refractory material isolates the metal ion pair LiMn in the refractory material 2 O 4 While isolating the LiMn 2 O 4 Corrosion and erosion of refractory materials by moderately basic compounds, sintered LiMn 2 O 4 The product percent of pass is improved by 8.7 percent, and each ton of LiMn 2 O 4 The energy is saved by 11.1 percent, and the service life of the roller kiln is prolonged by 0.6 time.
Comparative example 3
(1) Preparing an insulating material: lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed homogeneously in stoichiometric ratio to form La at the burning temperature of 1400 deg.c 2 (Zr 0.4 Ce 0.6 ) 2 O 7 Powder, 200 parts of the powder is added into 250 parts of water and 1 part of dispersant mixed solution, and the slurry is ground to D particle size by grinding (90) After 10.0 μm the slurry was transferred to a dispersion tank and 330 parts of Al (H) were slowly added 2 PO 4 ) 3 Uniformly mixing the solution to obtain an isolation material;
(2) And (3) performance comparison analysis: compared with the conventional pushed slab kiln, the pushed slab kiln for isolating the refractory material isolates the metal ions in the refractory material from LiFePO 4 While isolating LiFePO 4 Corrosion and erosion of refractory material by medium-alkaline compounds, sintering LiFePO 4 The product percent of pass is improved by 8.7 percent, and each ton of LiFePO 4 The energy is saved by 11.1 percent, and the service life of the pushed slab kiln is prolonged by 0.6 time.
Comparative example 4
(1) Preparing an insulating material: lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed homogeneously in stoichiometric ratio to form La at 1400 deg.c 2 (Zr 0.2 Ce 0.8 ) 2 O 7 Powder, 200 parts of the powder was added to a mixed solution of 130 parts of water and 0.4 part of a dispersant, and the slurry was ground to a particle size D by grinding (90) After 10.0 μm the slurry was transferred to a dispersion tank and 330 parts of Al (H) were slowly added 2 PO 4 ) 3 Uniformly mixing the solution to obtain an insulating material;
(2) And (3) performance comparison analysis: compared with the conventional roller kiln, the roller kiln for isolating the refractory material isolates the metal ion pairs LiNi in the refractory material 1-x-y Co x M y O 2 While isolating LiNi 1-x-y Co x M y O 2 Corrosion and erosion of refractory materials by medium-basic compounds, sintering of LiNi 1-x-y Co x M y O 2 The product percent of pass is improved by 12.5 percent, and each ton of LiNi 1-x-y Co x M y O 2 Energy saving of 14.1% and roller wayThe service life of the kiln is prolonged by 0.9 times.
TABLE 1 comparison of the results of examples 1 to 4
Figure BDA0003924356590000121
Figure BDA0003924356590000131
TABLE 2 comparison of results of comparative examples 1-4
Figure BDA0003924356590000132
The comparison shows that compared with the conventional sintering kiln, the sintering kiln for isolating the refractory material isolates the pollution of metal ions in the refractory material to the anode material, and also isolates the corrosion and corrosion of the alkaline compound of the anode material to the refractory material, in the embodiment 1-4 using the invention, the product qualification rate of the sintered anode material is improved by more than 10 percent, the energy is saved by more than 15 percent for each ton of the anode material, and the service life of the sintering kiln is prolonged by more than 1 time. In comparative example 1, the calcination of the powder was incomplete after the calcination temperature of the powder was lowered, resulting in sintering of LiCoO 2 The yield of the product is improved, and each ton of LiCoO 2 The energy saving rate and the service life improvement rate of the pusher kiln are reduced; in comparative example 2, the coating cracks after the binder addition is reduced, resulting in sintering of LiMn 2 O 4 The product percent of pass is improved, and each ton of LiMn 2 O 4 The energy rate is saved, and the service life improvement amount of the roller kiln is reduced; in comparative example 3, the increase in the amount of water added results in a decrease in the coating density, liFePO per ton 4 The energy saving rate and the service life improvement amount of the pusher kiln are both reduced; comparative example 4 in which the amount of the dispersant added was reduced, the powder was not uniformly dispersed in water, resulting in LiNi 1-x- y Co x M y O 2 The energy saving rate and the service life improvement amount of the roller kiln are both reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A method for improving the sintering quality of a lithium battery anode material by insulating a refractory material is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparation of insulation materials
Lanthanum carbonate, cerium carbonate and zirconyl carbonate are mixed according to La 2 (Zr 1-x Ce x ) 2 O 7 Mixing uniformly according to the stoichiometric ratio, wherein x =0.2-0.8, forming cerium-doped lanthanum zirconate solid solution powder at the firing temperature of 1400-1500 ℃, adding the powder into a mixed solution of water and a dispersing agent, wherein the mass ratio of the powder to the water is (1.2-2): 1, the adding amount of the dispersing agent is 3 per mill-1% of the mass of the powder, and grinding the particle size of the slurry to D through grinding (90) And (3) less than or equal to 10.0 mu m, and then uniformly mixing the slurry and the high-temperature adhesive according to the proportion of 1 (0.8-1.5) to obtain the insulating material.
(2) Isolated sintering kiln refractory material
Spraying a layer of insulating material on the surface of the refractory material, wherein the spraying thickness is 0.2-0.4mm, drying at room temperature, heating according to the drying program of a sintering kiln, keeping the temperature for 4 hours when the highest temperature reaches 1250 ℃, and firmly combining the insulating material and the refractory material together to obtain the sintering kiln with the insulating refractory material;
(3) Sintering of positive electrode material
And (3) putting the sagger filled with the lithium battery anode raw material into a sintering kiln isolated from refractory materials, and passing through a preheating zone, a high-temperature zone and a cooling zone to obtain anode material powder.
2. The method for improving the sintering quality of the lithium battery positive electrode material by using the insulating refractory material as claimed in claim 1, wherein the method comprises the following steps: the dispersant is one or a mixture of more than two of BYK190, RT-8040 and RT-8022.
3. Root of herbaceous plantsThe method for improving the sintering quality of the lithium battery positive electrode material by using the insulating refractory material as claimed in claim 1, wherein the method comprises the following steps: the high-temperature adhesive is Al (H) 2 PO 4 ) 3 。
4. The method for improving the sintering quality of the lithium battery positive electrode material by using the insulating refractory material according to claim 1, wherein the method comprises the following steps: in the step (2), before the insulating material is sprayed, refractory clay and dust are removed from the surfaces of the refractory materials of the kiln wall and the kiln top of the sintering kiln.
5. The method for improving the sintering quality of the lithium battery positive electrode material by using the insulating refractory material as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the temperature of the high-temperature zone of the sintering kiln for isolating the refractory material is controlled to be 800-850 ℃.
6. The method for improving the sintering quality of the lithium battery positive electrode material by using the insulating refractory material as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the sintering kiln is a pushed slab kiln or a roller kiln.
7. The method for improving the sintering quality of the lithium battery positive electrode material by using the insulating refractory material according to claim 1, wherein the method comprises the following steps: in the step (3), the lithium battery anode raw material is LiCoO 2 、LiMn 2 O 4 、LiFePO 4 Or LiNi 1-x-y Co x M y O 2 Wherein M = Mn, al.
CN202211368339.8A 2022-11-03 2022-11-03 Method for improving sintering quality of lithium battery positive electrode material by insulating refractory material Pending CN115579450A (en)

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