CN112142118B - Mixture for producing lithium cobaltate through 3D printing and preparation method and application thereof - Google Patents
Mixture for producing lithium cobaltate through 3D printing and preparation method and application thereof Download PDFInfo
- Publication number
- CN112142118B CN112142118B CN202010095421.2A CN202010095421A CN112142118B CN 112142118 B CN112142118 B CN 112142118B CN 202010095421 A CN202010095421 A CN 202010095421A CN 112142118 B CN112142118 B CN 112142118B
- Authority
- CN
- China
- Prior art keywords
- weight
- mixture
- parts
- lithium cobaltate
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a mixture for producing lithium cobaltate by 3D printing and a preparation method and application thereof. The invention combines the 3D printing forming technology with the lithium cobaltate battery material production technology, provides a new technical approach for the forming application of the lithium cobaltate mixture, and simultaneously, the high fineness, high elasticity, high activity and excellent dryness of the lithium cobaltate mixture can meet the raw material requirements of the 3D printing forming technology, and ensures that the printed lithium cobaltate production raw material has excellent uniformity and stability. The preparation method provided by the invention is simple and convenient, is beneficial to engineering popularization and application, and has good economic and social benefits.
Description
Technical Field
The invention relates to a battery material, in particular to a mixture for producing lithium cobaltate by 3D printing, a preparation method and application thereof, and belongs to the technical field of production of lithium cobaltate battery materials.
Background
Since the 21 st century, 3D printing technology has been widely used in the fields of medical treatment, construction, and manufacturing, and the like, in which specially processed raw materials are used as "ink" of a 3D printer, and products or intermediate products of different structures and shapes are printed out by precise control of a computer program. The 3D printing technology has remarkable advantages in construction and production under severe environments such as high temperature, high pressure and rich dust. The full-flow computer control and the mechanized production realize the high efficiency and the accuracy of the production, and are one of the development trends in the field of the self-contained manufacturing of the battery material industry in the future.
Compared with the traditional secondary batteries such as nickel-metal hydride batteries, nickel-cadmium batteries, lead-acid batteries and the like, the lithium ion secondary battery has the advantages of high energy density, large power density, long cycle life, environmental friendliness and the like, is widely applied to power supply production of mobile phones, digital cameras and notebook computers, and becomes a research focus of the new energy material industry. The production method of lithium cobaltate at the present stage is mainly a solid phase method, and the method comprises the steps of fully mixing powder raw materials of cobalt and lithium in a ball milling mode, a high-speed stirring mode and the like, and then carrying out high-temperature sintering, crushing, screening, iron removal and other processes to obtain the final lithium cobaltate product. The cobalt source material mainly comprises cobaltosic oxide, cobalt carbonate and cobalt hydroxide, and the lithium source material mainly comprises lithium carbonate and lithium hydroxide. The solid phase method has the main problems of uniform material mixing, nonuniform cloth, inconsistent air permeability and the like in industrialization, and the problems of product uniformity deviation and the like easily occur in subsequent lithium cobaltate production. The 3D printing technology adopts a fine computer control program, so that the uniformity and the accuracy of the production process can be realized; meanwhile, the uniformity of the mixture can be guaranteed by the aid of the same extrusion force in the 3D printing and forming process, and stability and yield of products are further improved. Therefore, there is a need to develop a mixture for 3D printing production of lithium cobaltate and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a mixture for producing lithium cobaltate by 3D printing and a preparation method and application thereof, wherein a 3D printing forming technology is combined with a lithium cobaltate battery material production technology, a new technical approach is provided for the forming application of the lithium cobaltate mixture, and meanwhile, the high fineness, the high elasticity and the high activity of the lithium cobaltate mixture and the excellent dryness can meet the raw material requirements of the 3D printing forming technology, and the printed lithium cobaltate production raw material has excellent uniformity and stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
according to a first embodiment of the invention, there is provided a mix for 3D printing production of lithium cobaltate, the mix comprising the following components: lithium carbonate, cobalt-containing compounds, titanium dioxide, molybdenum trioxide, cerium dioxide, and fibers.
Preferably, the content of each component in the mixture is as follows:
lithium carbonate: 40 to 80 parts by weight, preferably 50 to 70 parts by weight, more preferably 55 to 65 parts by weight.
A cobalt-containing compound: 20 to 60 parts by weight, preferably 30 to 50 parts by weight, more preferably 35 to 45 parts by weight.
Titanium dioxide: 0.01 to 3 parts by weight, preferably 0.03 to 2.5 parts by weight, more preferably 0.05 to 1.5 parts by weight.
Molybdenum trioxide: 0.01 to 3 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight.
Cerium oxide: 0.01 to 3 parts by weight, preferably 0.03 to 2 parts by weight, and more preferably 0.05 to 1 part by weight.
Fiber: 0.01 to 3 parts by weight, preferably 0.03 to 2.5 parts by weight, and more preferably 0.05 to 2 parts by weight.
Preferably, the lithium carbonate is battery grade lithium carbonate, and the percentage content of the lithium carbonate is greater than or equal to 99.3%, preferably greater than or equal to 99.5%, and more preferably greater than or equal to 99.8%.
Preferably, the cobalt-containing compound is selected from one or more of cobaltosic oxide, cobalt carbonate and cobalt hydroxide. Preferably cobaltosic oxide.
Preferably, the purity of the cobalt-containing compound is 95.0% or more, preferably 97.0% or more, and more preferably 99.0% or more.
Preferably, the titanium dioxide is nanoscale titanium dioxide.
Preferably, the titanium dioxide has a particle size of less than 500nm, preferably less than 400nm, more preferably less than 300 nm.
Preferably, the molybdenum trioxide is micron-sized molybdenum trioxide.
Preferably, the particle size of the molybdenum trioxide is less than 50 μm, preferably less than 40 μm, more preferably less than 30 μm.
Preferably, the ceria is micron-sized ceria.
Preferably, the particle size of the cerium oxide is less than 40 μm, preferably less than 35 μm, more preferably less than 30 μm.
Preferably, the fibers are polyolefin fibers, preferably high modulus polyolefin fibers, and more preferably polypropylene elastic fibers.
Preferably, the length of the fibres is from 0.1 to 100mm, preferably from 0.5 to 80mm, more preferably from 1 to 50 mm.
Preferably, the fiber thickness is 1 to 12dtex, preferably 1.5 to 10dtex, more preferably 2 to 8 dtex.
According to a second embodiment of the invention, there is provided a method of preparing a mix for use in 3D printing for the production of lithium cobaltate or a method of preparing a mix according to the first embodiment, the method comprising the steps of:
(1) mixing the cobalt-containing compound, lithium carbonate, titanium dioxide, molybdenum trioxide and cerium dioxide according to the weight ratio, and stirring for the first time to obtain the premix.
(2) Stirring the premix obtained in the step (1) for the second time; and adding fibers in the stirring process to obtain a mixture for producing lithium cobaltate by 3D printing.
Preferably, the stirring in step (1) is carried out in a batch container rotary-type mixer. The stirring time is more than or equal to 20min, preferably more than or equal to 50min, and more preferably more than or equal to 80 min.
Preferably, the addition of the fibers in the step (2) is a batch addition, and specifically comprises the following steps: the first batch of fiber was added and stirred. Adding the secondary fiber and stirring; … … add the n-th fiber and stir.
Preferably, n is from 2 to 30, preferably from 3 to 20, more preferably from 4 to 10.
According to a third embodiment of the invention, there is provided a mix according to the first embodiment or a mix prepared by the method according to the second embodiment, the mix being used for 3D printing for the production of lithium cobaltate.
According to a fourth embodiment of the present invention, there is provided a method for preparing lithium cobaltate, wherein the mixture material according to the first embodiment or the mixture material prepared by the method according to the second embodiment is printed by a 3D printer to obtain lithium cobaltate.
In the invention, the lithium carbonate, the cobalt-containing compound, the titanium dioxide, the molybdenum trioxide, the cerium dioxide, the fibers and the like are in a completely dry state, no water is needed to be added, and the materials are easy to adhere to balls after the water is added, so that segregation is formed, and the uniformity of the product is influenced. Meanwhile, the roasting of the lithium cobaltate adopts an electric heating process, and potential hazards in the aspects of water and electric contact exist after water is added.
In the invention, the nano-scale titanium dioxide is adopted because the titanium dioxide has super-hydrophilic surface and strong adhesive force, so that the overall adhesive force of the mixture can be increased, the tensile strength of the material is improved, the elongation at break is reduced, and the mixture becomes a qualified 3D printing raw material.
In the invention, micron-sized molybdenum trioxide is adopted to solve the characteristic that raw material lithium carbonate is easy to decompose in the high-temperature roasting process to form a large number of pores, and the pores generated by the decomposition of lithium carbonate are intercalated by utilizing the phase structure characteristics (orthorhombic or orthorhombic phase, metastable monoclinic phase and hexagonal phase) of the molybdenum trioxide, so that the whole material forms a framework structure, and the overall strength and rigidity of the material are improved.
In the invention, the micron-sized cerium dioxide is adopted because the preparation process of the lithium cobaltate is lack of water as a lubricant, and the cerium dioxide is an excellent material lubricant and can improve the lubrication coefficient of the material. Meanwhile, the forming process of the lithium cobaltate can be improved, the product is promoted to be preferentially oriented, and the lithium cobaltate is more uniform and compact. The cerium dioxide can reduce the roasting temperature of lithium cobaltate, inhibit the growth of crystal lattices and improve the compactness of materials.
In the present invention, polyolefin elastic fibers (for example, polypropylene elastic fibers having a length of 5 to 50mm, preferably 8 to 30mm, more preferably 10 to 20mm, and a thickness of 0.5 to 15dtex, preferably 1 to 12dtex, more preferably 2 to 10dtex) are substances composed of continuous or discontinuous filaments, and play an important role in terms of maintenance and binding, and the addition of the fibers is effective in improving the strength, rigidity and elasticity of the blend. Meanwhile, the fiber can form a good bonding interface in the mixture, so that the bonding strength of the mixture is improved, and the requirement of the 3D printing raw material is met. The need for batch additions to add polyolefin fibers is mainly two objectives: firstly, the method is matched with a lithium cobaltate preparation process, and a mixing process for preparing the lithium cobaltate belongs to multi-stage mixing, and batch addition is matched with mixing times. Secondly, 3D printing additives are more, the mixing difficulty is high, the mixing effect can be enhanced by adding the additives in batches, and the uniformity of the mixture is improved. There are two requirements to the timing of the fiber input: one is a small number of times, added in portions. Secondly, the two components are added in different stages of the mixing process (generally the front end, the middle end and the tail end of the mixer). The mixing process has long flow, different mixing process functions are different, and the control of the input time has great influence on the full mixing of the mixture, especially the additives prepared from the power-assisted 3D printing raw materials.
Compared with the prior art, the invention has the following beneficial technical effects:
1: according to the invention, the lithium cobaltate production technology and the 3D printing technology are combined, and the fineness, elasticity and activity of the mixture are improved by optimizing the formula of the mixture for producing the lithium cobaltate, so that the mixture meets the raw material requirements of 3D printing. The invention provides a new technical approach for applying a raw material mixture for producing lithium cobaltate, which can realize the uniformity and the accuracy of a lithium cobaltate production process by adopting a fine 3D printing computer program control technology.
2: the invention adopts uniform extrusion force in the 3D printing process, can effectively improve the uniformity of the material distribution and the consistency of the air permeability of the mixture, solves the problem of large product index fluctuation in the production process of lithium cobaltate, and further improves the stability and the qualification rate of products. The preparation method provided by the invention is simple and convenient, and has good engineering popularization and application prospects. The development of intelligent preparation and accurate preparation technology in the field of battery materials in the future is considered, and the popularization of the method has good economic and social benefits.
Detailed Description
The technical solutions of the present invention are illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
A mixture for 3D printing to produce lithium cobaltate, the mixture comprising the following components: lithium carbonate, cobalt-containing compounds, titanium dioxide, molybdenum trioxide, cerium dioxide, and fibers.
Preferably, the content of each component in the mixture is as follows:
lithium carbonate: 40 to 80 parts by weight, preferably 50 to 70 parts by weight, more preferably 55 to 65 parts by weight.
A cobalt-containing compound: 20 to 60 parts by weight, preferably 30 to 50 parts by weight, more preferably 35 to 45 parts by weight.
Titanium dioxide: 0.01 to 3 parts by weight, preferably 0.03 to 2.5 parts by weight, more preferably 0.05 to 1.5 parts by weight.
Molybdenum trioxide: 0.01 to 3 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight.
Cerium oxide: 0.01 to 3 parts by weight, preferably 0.03 to 2 parts by weight, and more preferably 0.05 to 1 part by weight.
Fiber: 0.01 to 3 parts by weight, preferably 0.03 to 2.5 parts by weight, and more preferably 0.05 to 2 parts by weight.
Preferably, the lithium carbonate is battery grade lithium carbonate, and the percentage content of the lithium carbonate is greater than or equal to 99.3%, preferably greater than or equal to 99.5%, and more preferably greater than or equal to 99.8%.
Preferably, the cobalt-containing compound is selected from one or more of cobaltosic oxide, cobalt carbonate and cobalt hydroxide. Preferably cobaltosic oxide.
Preferably, the purity of the cobalt-containing compound is 95.0% or more, preferably 97.0% or more, and more preferably 99.0% or more.
Preferably, the titanium dioxide is nanoscale titanium dioxide.
Preferably, the titanium dioxide has a particle size of less than 500nm, preferably less than 400nm, more preferably less than 300 nm.
Preferably, the molybdenum trioxide is micron-sized molybdenum trioxide.
Preferably, the particle size of the molybdenum trioxide is less than 50 μm, preferably less than 40 μm, more preferably less than 30 μm.
Preferably, the ceria is micron-sized ceria.
Preferably, the particle size of the cerium oxide is less than 40 μm, preferably less than 35 μm, more preferably less than 30 μm.
Preferably, the fibers are polyolefin fibers, preferably high modulus polyolefin fibers.
Preferably, the length of the fibres is from 0.1 to 100mm, preferably from 0.5 to 80mm, more preferably from 1 to 50 mm.
Preferably, the fiber thickness is 1 to 12dtex, preferably 1.5 to 10dtex, more preferably 2 to 8 dtex.
Example 1
Weighing 38.0 parts of cobaltosic oxide, 58.0 parts of battery-grade lithium carbonate, 0.6 part of nano-grade titanium dioxide, 0.6 part of micron-grade molybdenum trioxide and 0.7 part of micron-grade cerium dioxide according to proportion, and uniformly mixing for the first time in a batch container rotary mixer for 60min to obtain the premix. And then measuring 1.0 part of polypropylene elastic fiber, uniformly mixing for the second time in a powerful mixer for 60min, adding the polypropylene elastic fiber in batches for 5 times in the uniformly mixing process, and finally obtaining the lithium cobaltate mixture meeting the production requirements. Wherein the grain size range of the nano-scale titanium dioxide is less than or equal to 120nm, the grain size range of the micron-scale molybdenum trioxide is less than or equal to 20 mu m, the grain size range of the micron-scale cerium dioxide is less than or equal to 12 mu m, the length of the polypropylene elastic fiber is 6.0mm, and the fiber thickness is 4.0 dtex.
Meanwhile, a lithium cobaltate comparison test prepared from a mixture which does not adopt a 3D printing technology and a mixture which adopts the 3D printing technology is developed. Under the conditions that the roasting temperature is 950 ℃ and the roasting time is 18 hours, the electrochemical performance of the lithium cobaltate obtained without adopting the 3D printing technology is 4.0V, and the specific surface area is 0.32m2(ii)/g, compacted density of 3.9g/cm3(ii) a The electrochemical performance of the lithium cobaltate obtained by adopting the 3D printing technology is 4.4V, and the specific surface area is 0.39m2(ii)/g, compacted density 4.6g/cm3. The quality of the product is improved, and the feasibility and certain advantages of the 3D printing technology in the field of lithium cobaltate preparation are demonstrated.
Example 2
40.0 parts of cobaltosic oxide, 60.0 parts of battery-grade lithium carbonate, 0.5 part of nano-grade titanium dioxide, 0.6 part of micron-grade molybdenum trioxide and 0.6 part of micron-grade cerium dioxide are weighed according to proportion, and are mixed for the first time in a batch container rotary mixer for 60min to obtain a premix. And then measuring 1.0 part of polypropylene elastic fiber, uniformly mixing for the second time in a powerful mixer for 60min, adding the polypropylene elastic fiber in batches for 5 times in the uniformly mixing process, and finally obtaining the lithium cobaltate mixture meeting the production requirements. Wherein the grain size range of the nano-scale titanium dioxide is less than or equal to 120nm, the grain size range of the micron-scale molybdenum trioxide is less than or equal to 20 mu m, the grain size range of the micron-scale cerium dioxide is less than or equal to 12 mu m, the length of the polypropylene elastic fiber is 6.0mm, and the fiber thickness is 4.0 dtex.
Meanwhile, the technology of not adopting 3D printing and the technology of adopting 3D printing are developedThe mixture of the technique was used to prepare a lithium cobaltate comparative test. Under the conditions that the roasting temperature is 950 ℃ and the roasting time is 18 hours, the electrochemical performance of the lithium cobaltate obtained without adopting the 3D printing technology is 3.9V, and the specific surface area is 0.30m2(ii)/g, compacted density of 3.8g/cm3(ii) a The electrochemical performance of the lithium cobaltate obtained by adopting the 3D printing technology is 4.2V, and the specific surface area is 0.37m2(ii)/g, compacted density 4.4g/cm3. The quality of the product is improved, and the feasibility and certain advantages of the 3D printing technology in the field of lithium cobaltate preparation are demonstrated.
Example 3
Weighing 50.0 parts of cobaltosic oxide, 70.0 parts of battery-grade lithium carbonate, 0.3 part of nano-grade titanium dioxide, 0.4 part of micron-grade molybdenum trioxide and 0.4 part of micron-grade cerium dioxide according to a proportion, and uniformly mixing for the first time in a batch container rotary mixer for 50min to obtain the premix. And then weighing 0.8 part of polypropylene elastic fiber, uniformly mixing for the second time in a powerful mixer for 50min, adding the polypropylene elastic fiber in batches for 4 times in the uniformly mixing process, and finally obtaining the lithium cobaltate mixture meeting the production requirements. Wherein the grain diameter range of the nano-titanium dioxide is less than or equal to 150nm, the grain diameter range of the micron molybdenum trioxide is less than or equal to 25 mu m, the grain diameter range of the micron cerium dioxide is less than or equal to 15 mu m, the length of the polypropylene elastic fiber is 8.0mm, and the thickness of the fiber is 5.0 dtex.
Meanwhile, a comparison test for preparing lithium cobaltate by using a mixture which does not adopt a 3D printing technology and adopts a 3D printing technology is developed. Under the conditions of the roasting temperature of 1050 ℃ and the roasting time of 12 hours, the electrochemical performance of the lithium cobaltate obtained without adopting the 3D printing technology is 3.8V, and the specific surface area is 0.29m2(ii)/g, compacted density of 3.8g/cm3(ii) a The electrochemical performance of the lithium cobaltate obtained by adopting the 3D printing technology is 4.0V, and the specific surface area is 0.33m2(ii)/g, compacted density 4.0g/cm3. The quality of the product is improved, and the feasibility and certain advantages of the 3D printing technology in the field of lithium cobaltate preparation are demonstrated.
Example 4
55.0 parts of cobaltosic oxide, 75.0 parts of battery-grade lithium carbonate, 0.2 part of nano-grade titanium dioxide, 0.3 part of micron-grade molybdenum trioxide and 0.1 part of micron-grade cerium dioxide are measured in proportion, and are mixed uniformly for the first time in a batch container rotary mixer for 45min to obtain the premix. And then weighing 0.4 part of polypropylene elastic fiber, uniformly mixing in a powerful mixer for the second time for 45min, adding the polypropylene elastic fiber in batches for 3 times in the uniformly mixing process, and finally obtaining the lithium cobaltate mixture meeting the production requirements. Wherein the grain size range of the nano-scale titanium dioxide is less than or equal to 100nm, the grain size range of the micron-scale molybdenum trioxide is less than or equal to 20 mu m, the grain size range of the micron-scale cerium dioxide is less than or equal to 18 mu m, the length of the polypropylene elastic fiber is 10.0mm, and the fiber thickness is 6.0 dtex.
Meanwhile, a lithium cobaltate comparison test prepared from a mixture which does not adopt a 3D printing technology and a mixture which adopts the 3D printing technology is developed. Under the conditions of the roasting temperature of 1000 ℃ and the roasting time of 15h, the electrochemical performance of the lithium cobaltate obtained without adopting the 3D printing technology is 3.9V, and the specific surface area is 0.30m2Per g, the compacted density is 3.8g/cm3(ii) a The electrochemical performance of the lithium cobaltate obtained by adopting the 3D printing technology is 4.2V, and the specific surface area is 0.36m2(ii)/g, compacted density 4.3g/cm3. The quality of the product is improved, and the feasibility and certain advantages of the 3D printing technology in the field of lithium cobaltate preparation are demonstrated.
Example 5
60.0 parts of cobaltosic oxide, 80.0 parts of battery-grade lithium carbonate, 0.3 part of nano-grade titanium dioxide, 0.4 part of micron-grade molybdenum trioxide and 0.15 part of micron-grade cerium dioxide are measured in proportion, and are mixed uniformly for the first time in a batch container rotary mixer for 45min to obtain the premix. Then measuring 0.6 part of polypropylene elastic fiber, carrying out secondary mixing in an intensive mixer for 45min, adding the polypropylene elastic fiber in batches for 3 times in the mixing process, and finally obtaining the lithium cobaltate mixture meeting the production requirement. Wherein the grain size range of the nano-scale titanium dioxide is less than or equal to 100nm, the grain size range of the micron-scale molybdenum trioxide is less than or equal to 20 mu m, the grain size range of the micron-scale cerium dioxide is less than or equal to 18 mu m, the length of the polypropylene elastic fiber is 10.0mm, and the fiber thickness is 6.0 dtex.
At the same timeAnd a lithium cobaltate comparison test prepared by using a mixture without adopting a 3D printing technology and a mixture adopting the 3D printing technology is developed. Under the conditions that the roasting temperature is 1000 ℃ and the roasting time is 15 hours, the electrochemical performance of the lithium cobaltate obtained without adopting the 3D printing technology is 3.7V, and the specific surface area is 0.28m2G, compacted density of 3.5/cm3(ii) a The electrochemical performance of the lithium cobaltate obtained by adopting the 3D printing technology is 3.9V, and the specific surface area is 0.35m2(ii)/g, compacted density 4.0g/cm3. The quality of the product is improved, and the feasibility and certain advantages of the 3D printing technology in the field of lithium cobaltate preparation are demonstrated.
Example 6
55.0 parts of cobaltosic oxide, 65.0 parts of battery-grade lithium carbonate, 0.35 part of nano-grade titanium dioxide, 0.4 part of micron-grade molybdenum trioxide and 0.5 part of micron-grade cerium dioxide are measured in proportion, and are mixed uniformly for the first time in a batch container rotary mixer for 50min to obtain the premix. And then weighing 0.8 part of polypropylene elastic fiber, uniformly mixing for the second time in a powerful mixer for 50min, adding the polypropylene elastic fiber in batches for 4 times in the uniformly mixing process, and finally obtaining the lithium cobaltate mixture meeting the production requirements. Wherein the grain size range of the nano-scale titanium dioxide is less than or equal to 150nm, the grain size range of the micron-scale molybdenum trioxide is less than or equal to 25 mu m, the grain size range of the micron-scale cerium dioxide is less than or equal to 15 mu m, the length of the polypropylene elastic fiber is 8.0mm, and the fiber thickness is 5.0 dtex.
Meanwhile, a lithium cobaltate comparison test prepared from a mixture which does not adopt a 3D printing technology and a mixture which adopts the 3D printing technology is developed. Under the conditions of the roasting temperature of 1050 ℃ and the roasting time of 12 hours, the electrochemical performance of the lithium cobaltate obtained without adopting the 3D printing technology is 3.9V, and the specific surface area is 0.30m2(ii)/g, compacted density of 3.8g/cm3(ii) a The electrochemical performance of the lithium cobaltate obtained by adopting the 3D printing technology is 4.2V, and the specific surface area is 0.35m2(ii)/g, compacted density 4.2g/cm3. The quality of the product is improved, and the feasibility and certain advantages of the 3D printing technology in the field of lithium cobaltate preparation are demonstrated.
Example 7
57.0 parts of cobalt carbonate, 75.0 parts of battery-grade lithium carbonate, 0.2 part of nano-grade titanium dioxide, 0.3 part of micron-grade molybdenum trioxide and 0.1 part of micron-grade cerium dioxide are weighed according to proportion, and are mixed uniformly for the first time in a batch container rotary mixer for 45min to obtain the premix. And then weighing 0.4 part of polypropylene elastic fiber, uniformly mixing in a powerful mixer for the second time for 45min, adding the polypropylene elastic fiber in batches for 3 times in the uniformly mixing process, and finally obtaining the lithium cobaltate mixture meeting the production requirements. Wherein the grain size range of the nano-scale titanium dioxide is less than or equal to 100nm, the grain size range of the micron-scale molybdenum trioxide is less than or equal to 20 mu m, the grain size range of the micron-scale cerium dioxide is less than or equal to 18 mu m, the length of the polypropylene elastic fiber is 10.0mm, and the fiber thickness is 6.0 dtex.
Meanwhile, a lithium cobaltate comparison test prepared from a mixture which does not adopt a 3D printing technology and a mixture which adopts the 3D printing technology is developed. Under the conditions of the roasting temperature of 1000 ℃ and the roasting time of 15h, the electrochemical performance of the lithium cobaltate obtained without adopting the 3D printing technology is 3.9V, and the specific surface area is 0.30m2(ii)/g, compacted density of 3.8g/cm3(ii) a The electrochemical performance of the lithium cobaltate obtained by adopting the 3D printing technology is 4.1V, and the specific surface area is 0.35m2(ii)/g, compacted density 4.2g/cm3. The quality of the product is improved, and the feasibility and certain advantages of the 3D printing technology in the field of lithium cobaltate preparation are demonstrated.
Example 8
50.0 parts of cobalt hydroxide, 75.0 parts of battery-grade lithium carbonate, 0.2 part of nano-grade titanium dioxide, 0.3 part of micron-grade molybdenum trioxide and 0.1 part of micron-grade cerium dioxide are weighed according to proportion, and are mixed uniformly for the first time in a batch container rotary mixer for 45min to obtain the premix. And then weighing 0.4 part of polypropylene elastic fiber, uniformly mixing in a powerful mixer for the second time for 45min, adding the polypropylene elastic fiber in batches for 3 times in the uniformly mixing process, and finally obtaining the lithium cobaltate mixture meeting the production requirements. Wherein the grain size range of the nano-scale titanium dioxide is less than or equal to 100nm, the grain size range of the micron-scale molybdenum trioxide is less than or equal to 20 mu m, the grain size range of the micron-scale cerium dioxide is less than or equal to 18 mu m, the length of the polypropylene elastic fiber is 10.0mm, and the fiber thickness is 6.0 dtex.
Meanwhile, a lithium cobaltate comparison test prepared from a mixture which does not adopt a 3D printing technology and a mixture which adopts the 3D printing technology is developed. Under the conditions of the roasting temperature of 1000 ℃ and the roasting time of 15h, the electrochemical performance of the lithium cobaltate obtained without adopting the 3D printing technology is 3.9V, and the specific surface area is 0.30m2Per g, the compacted density is 3.8g/cm3(ii) a The electrochemical performance of the lithium cobaltate obtained by adopting the 3D printing technology is 4.3V, and the specific surface area is 0.38m2(ii)/g, compacted density 4.5g/cm3. The quality of the product is improved, and the feasibility and certain advantages of the 3D printing technology in the field of lithium cobaltate preparation are demonstrated.
The above embodiments are merely illustrative of the principles and effects of the present invention, and are not to be construed as limiting the invention. Modifications and variations can be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the present invention. Accordingly, it is intended that all modifications and variations that fall within the scope of the invention without departing from the spirit of the invention be embraced by the claims.
Claims (22)
1. The mixture for producing lithium cobaltate through 3D printing is characterized in that: the mixture comprises the following components: lithium carbonate, cobalt-containing compounds, titanium dioxide, molybdenum trioxide, cerium dioxide, and fibers;
wherein: the lithium carbonate is battery-grade lithium carbonate, and the percentage content of the lithium carbonate is more than or equal to 99.3%; the cobalt-containing compound is selected from one or more of cobaltosic oxide, cobalt carbonate and cobalt hydroxide; the purity of the cobalt-containing compound is more than or equal to 95.0 percent; the titanium dioxide is nano-scale titanium dioxide; the molybdenum trioxide is micron-sized molybdenum trioxide; the cerium dioxide is micron-sized cerium dioxide; the fibers are polyolefin fibers.
2. The mix of claim 1, wherein: the content of each component in the mixture is as follows: lithium carbonate: 40-80 parts by weight; a cobalt-containing compound: 20-60 parts by weight; titanium dioxide: 0.01-3 parts by weight; molybdenum trioxide: 0.01-3 parts by weight; cerium oxide: 0.01-3 parts by weight; fiber: 0.01-3 parts by weight.
3. The mix of claim 1, wherein: the content of each component in the mixture is as follows: lithium carbonate: 50-70 parts by weight; a cobalt-containing compound: 30-50 parts by weight; titanium dioxide: 0.03-2.5 parts by weight; molybdenum trioxide: 0.03-2 parts by weight; cerium oxide: 0.03-2 parts by weight; fiber: 0.03-2.5 weight portions.
4. The mix of claim 1, wherein: the content of each component in the mixture is as follows: lithium carbonate: 55-65 parts by weight; a cobalt-containing compound: 35-45 parts by weight; titanium dioxide: 0.05 to 1.5 weight portions; molybdenum trioxide: 0.05 to 1.5 weight portions; cerium oxide: 0.05-1 weight part; fiber: 0.05-2 parts by weight.
5. The mix according to any one of claims 1 to 4, characterized in that: the percentage content of the lithium carbonate is more than or equal to 99.5 percent; and/or
The purity of the cobalt-containing compound is more than or equal to 97.0 percent.
6. The mix of claim 5, wherein: the percentage content of the lithium carbonate is more than or equal to 99.8 percent; and/or
The purity of the cobalt-containing compound is more than or equal to 99.0%.
7. The mix according to any of claims 1-4, 6, wherein: the cobalt-containing compound is selected to be cobaltosic oxide; and/or
The particle size of the titanium dioxide is less than 500 nm; and/or
The particle size of the molybdenum trioxide is less than 50 mu m; and/or
The particle size of the cerium oxide is less than 40 μm.
8. The mix of claim 7, wherein: the particle size of the titanium dioxide is less than 400 nm; and/or
The particle size of the molybdenum trioxide is less than 40 mu m; and/or
The particle size of the cerium oxide is less than 35 μm.
9. The mix of claim 7, wherein: the particle size of the titanium dioxide is less than 300 nm; and/or
The particle size of the molybdenum trioxide is less than 30 mu m; and/or
The particle size of the cerium oxide is less than 30 μm.
10. The mixture for producing lithium cobaltate according to any one of claims 1 to 4, 6 and 8 to 9, wherein: the fiber is high elastic modulus polyolefin fiber.
11. The mixture for producing lithium cobaltate according to claim 10, wherein: the length of the fiber is 0.1-100 mm; the thickness of the fiber is 1 to 12 dtex.
12. The mixture for producing lithium cobaltate according to claim 10, wherein: the length of the fiber is 0.5-80 mm; the thickness of the fiber is 1.5-10 dtex.
13. The mixture for producing lithium cobaltate according to claim 10, wherein: the length of the fiber is 1-50 mm; the thickness of the fiber is 2-8 dtex.
14. A method of preparing a mix according to any one of claims 1 to 13, comprising the steps of:
(1) mixing a cobalt-containing compound, lithium carbonate, titanium dioxide, molybdenum trioxide and cerium dioxide according to a weight ratio, and stirring for the first time to obtain a premix;
(2) stirring the premix obtained in the step (1) for the second time; adding fibers in the stirring process to obtain a mixture for producing lithium cobaltate by 3D printing; the addition of the fibers is batch-wise addition, and specifically comprises the following steps: adding the first batch of fibers and stirring; adding the secondary fiber and stirring; … … adding the n-th fiber and stirring.
15. The method of claim 14, wherein: the stirring in the step (1) is carried out in a batch container rotary mixer; the stirring time is more than or equal to 20 min.
16. The method of claim 15, wherein: the stirring time in the step (1) is more than or equal to 50 min.
17. The method of claim 15, wherein: the stirring time in the step (1) is more than or equal to 80 min.
18. The method according to any one of claims 14-17, wherein: n is 2 to 30.
19. The method of claim 18, wherein: n is 3 to 20.
20. The method of claim 18, wherein: n is 4-10.
21. The mix prepared according to the process of any one of claims 14 to 20, characterized in that: and the mixture is used for 3D printing to produce lithium cobaltate.
22. A preparation method of lithium cobaltate is characterized by comprising the following steps: printing the mixture prepared by the method of any one of claims 14 to 20 through a 3D printer to obtain lithium cobaltate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010095421.2A CN112142118B (en) | 2020-02-17 | 2020-02-17 | Mixture for producing lithium cobaltate through 3D printing and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010095421.2A CN112142118B (en) | 2020-02-17 | 2020-02-17 | Mixture for producing lithium cobaltate through 3D printing and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112142118A CN112142118A (en) | 2020-12-29 |
| CN112142118B true CN112142118B (en) | 2022-05-03 |
Family
ID=73891837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010095421.2A Active CN112142118B (en) | 2020-02-17 | 2020-02-17 | Mixture for producing lithium cobaltate through 3D printing and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112142118B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102427134A (en) * | 2011-12-02 | 2012-04-25 | 湘潭大学 | Mixed conductor composite material LiFePO4-MXy and preparation method thereof |
| CN104241627A (en) * | 2014-09-11 | 2014-12-24 | 北大先行科技产业有限公司 | Lithium cobaltate for positive electrode of lithium ion battery and preparation method of lithium cobaltate for positive electrode of lithium ion battery |
| CN110336006B (en) * | 2019-07-04 | 2022-07-12 | 中国科学院青岛生物能源与过程研究所 | Lithium cobaltate cathode material with high structural stability and preparation method thereof |
| CN110627128B (en) * | 2019-09-11 | 2020-11-17 | 湖南金富力新能源股份有限公司 | Lithium manganate positive electrode material, preparation method and application |
| CN111354946B (en) * | 2020-03-11 | 2021-05-18 | 宁德新能源科技有限公司 | Positive electrode material, and electrochemical device and electronic device using same |
-
2020
- 2020-02-17 CN CN202010095421.2A patent/CN112142118B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112142118A (en) | 2020-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107331862B (en) | A kind of sum method conducive to the deep cycle battery lead plaster for generating 4BS | |
| CN108923041B (en) | Ternary cathode material, preparation method thereof and lithium ion battery | |
| CN108172825B (en) | High-voltage high-compaction low-cost lithium cobalt oxide positive electrode material and preparation method thereof | |
| CN103441252A (en) | Method for preparing lithium-enriched manganese-based anode material of nano-oxide-coated lithium ion battery | |
| CN102701288A (en) | Perovskite composite oxide LaFeO3 monodisperse micrometer hollow balls and preparation method thereof | |
| CN107046126B (en) | Preparation method of superfine metal oxide/graphene two-dimensional negative electrode composite material | |
| CN105355985B (en) | The preparation method of nano silicon oxide dispersion liquid and preparation method thereof and biscuit | |
| CN105720266A (en) | Lead paste for high-performance lead-acid storage battery | |
| CN106910872B (en) | A kind of positive plate of lead storage battery and preparation method thereof | |
| CN110247107A (en) | A kind of solid electrolyte, and its preparation method and application | |
| CN103482674A (en) | Preparation method of copper oxide nanowires and application of copper oxide nanowires in negative electrode of lithium ion battery | |
| CN103042230A (en) | Preparation method for micron spherical silver powder for electronic paste | |
| CN112885992A (en) | Preparation method and application of lithium ion battery negative electrode material | |
| DE112021005980T5 (en) | PROCESS FOR THE PRODUCTION OF NANO-SIZED LITHIUM-COBALT OXIDE CATHODE MATERIAL AND ITS USE | |
| CN109244464A (en) | A kind of graphene anode sizing agent and efficient controllable method for preparing | |
| CN112142118B (en) | Mixture for producing lithium cobaltate through 3D printing and preparation method and application thereof | |
| CN108987741B (en) | Nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN110336074A (en) | A kind of oxynitride solid electrolyte and its preparation method and application | |
| CN114195204A (en) | High-sphericity manganese-rich carbonate precursor and preparation method and application thereof | |
| CN110655105B (en) | Preparation method of tetrabasic lead sulfate | |
| CN109250697B (en) | Low-cost high-purity green environment-friendly nanocrystalline battery-grade anhydrous FePO4Preparation method of (1) | |
| CN108448082B (en) | Electrode material, petal-shaped porous structure iron-based composite oxide thereof and preparation method thereof | |
| CN107777718B (en) | A kind of Y2O3Nano-powder and preparation method thereof | |
| CN115084516B (en) | Preparation method of boron-based multi-element composite material | |
| CN112125347B (en) | Low-energy-consumption rapid preparation method of lithium cobaltate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |