CN111960467B - Preparation process of multi-element material - Google Patents
Preparation process of multi-element material Download PDFInfo
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- CN111960467B CN111960467B CN202010876806.2A CN202010876806A CN111960467B CN 111960467 B CN111960467 B CN 111960467B CN 202010876806 A CN202010876806 A CN 202010876806A CN 111960467 B CN111960467 B CN 111960467B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
Abstract
The invention discloses a preparation process of a multi-element material, which comprises the following steps: (1) Preparing required raw materials, uniformly mixing the raw materials to obtain a mixture, wherein no solvent is added in the mixing process of the raw materials; (2) granulating and crushing the mixture to obtain powder; (3) Sintering the powder under set conditions to obtain the multi-element material. The process can realize the tight combination of various elements, reduce the diffusion distance of various elements during sintering, fully react the elements and obtain a final product which accords with the expectation.
Description
Technical Field
The invention relates to the field of material sintering treatment, in particular to a preparation process of a multi-element material.
Background
The full-flow sintering process of the multi-element inorganic material generally comprises the steps of 'batching-mixing- (drying) -sintering-collecting'. In each step, the uniformity of the mixed materials greatly influences the purity of the subsequent sintering materials; in addition, the bonding force between various elements is also an important factor. The common mixing adopts a wet mixing method, namely a liquid phase solvent is adopted as a grinding aid to realize the uniform mixing of various materials; however, the big disadvantage brought by wet mixing is the difficult recovery problem of the liquid phase solvent, especially when the solvent is an organic solvent which is easy to explode and is toxic, the whole process is lengthened and the operation is complicated, and hidden troubles and problems in the aspects of environmental protection and safety also exist. In contrast, dry mixing is performed without a solvent, and has certain advantages over wet mixing, but dry mixing generally has difficulty in obtaining a desired product in a subsequent sintering step due to problems of mixing uniformity, binding force among multiple elements, and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a preparation process of the multielement material, the preparation process can realize the tight combination of various elements without using a liquid phase solvent as a grinding aid, the diffusion distance of various elements during sintering can be reduced, the elements can be fully reacted, and a final product which has the same material mixing effect as a wet method and has better compactness and dispersion degree is obtained.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation process of a multi-element material comprises the following steps:
(1) Preparing required raw materials, and uniformly mixing a lithium-containing raw material and other element raw materials to obtain a mixture, wherein no solvent is added in the mixing process of the raw materials;
(2) Granulating and crushing the mixture to obtain powder;
(3) And sintering the powder under a set condition to obtain the multielement material.
The design idea of the technical scheme is that in the prior art, the raw materials are generally mixed by using a wet method and then sintered, but the problems of recovery of liquid phase solution, environmental protection and safety exist in the process of mixing by using the wet method, so that the process is prolonged, and the requirements of the sintering process on the dispersibility and compactness of each element cannot be met by mixing the raw materials by using the dry method; the invention realizes the tight combination of a plurality of elements by granulating the mixture after the dry mixing of the raw materials, thereby reducing the diffusion distance of each element during sintering, leading each element to be fully reacted and forming a final target phase.
Based on the same technical concept, the invention also provides a preparation process of the multielement material, which comprises the following steps:
(1) Uniformly mixing the other element raw materials to obtain a mixture, wherein no solvent is added in the mixing process of the other element raw materials;
(2) Granulating and crushing the mixture to obtain powder;
(3) And uniformly mixing the powder with a lithium-containing raw material and sintering under a set condition to obtain the multi-element material.
The design idea of the technical scheme is that the lithium-containing raw material and other element raw materials are separately mixed, and the method is mainly based on the following considerations: firstly, the requirement for mixing the lithium-containing raw materials is lower in the preparation process of the multielement material, so that the workload of granulation operation can be reduced and the cost consumption is reduced by separately mixing the lithium-containing raw materials and other element raw materials; secondly, the lithium-containing raw material and other element raw materials are respectively mixed, so that the phenomenon that the lithium salt wrapped in the particles cannot be completely reacted can be avoided, and the reactivity of the lithium salt is improved.
Preferably, in the above aspect, the particle size of the lithium-containing raw material and the other element raw material is 0.01 μm to 10 μm. The granularity of raw materials is limited in the range, the mixing effect of the raw materials can be guaranteed, the gaps among the raw material particles are reduced, the compactness of the granulated particles is improved, and the compactness and the dispersion degree of a final product are facilitated.
In the above aspect, the particle size D50 of the powder in the step (2) is preferably 1 to 100 μm, and the particle size D90 is preferably 50 to 150 μm. The particle size of the powder is limited within the range, so that the condition that substances in the particles can not completely react during sintering due to overlarge particles after granulation can be avoided.
Preferably, in the step (2), the granulation process is a die granulation or isostatic pressing granulation process. The two granulation methods are simple and convenient to operate, simple in equipment and beneficial to industrialization of the process.
Preferably, in the above technical means, the pressure of the granulation operation in the step (2) is 2 to 200MPa. Further preferably, the pressure of the granulation operation in the step (2) is 10 to 100MPa; as a further preferred option, the pressure of the granulation operation in step (2) is between 50 and 100MPa. Too small pressure intensity can cause the compactness among all elements not to reach the standard, and too large pressure intensity can cause the granules to be difficult to break after granulation, thereby improving the cost and reducing the efficiency.
Preferably, in the step (3), the sintering condition of the powder is to keep the temperature of the powder at 500-1200 ℃ for 2-16 h.
Preferably, the lithium-containing material and the other element materials are one or more of oxides, sulfides, phosphates, oxalates, carbonates, acetates, hydroxides and halides.
Preferably, the mixing of the raw materials in step (1) is performed by one or more of an inclined type cylinder mixer, a twin-screw conical mixer and a high-speed mixer.
Preferably, the crushing operation of the mixture in the step (2) is performed by one or more of a jaw crusher, a hammer crusher, a roller crusher, a jet mill, a high-speed mixer and a mechanical crusher.
Compared with the prior art, the invention has the advantages that: the process can realize the tight combination of various elements, reduce the diffusion distance of various elements during sintering, fully react the elements and obtain a final product which accords with the expectation.
Drawings
FIG. 1 is an electron micrograph of mix A of example 1;
FIG. 2 is an electron micrograph of the powder of example 1;
FIG. 3 is an electron micrograph of a compound B in example 1;
FIG. 4 is an X-ray diffraction spectrum of the final products of example 1, comparative example 1 and comparative example 2.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
Example 1:
the preparation process of the multielement material of the embodiment comprises the following steps:
(1) 1006.73g of lanthanum oxide (with the particle size of 500 nm), 345.36g of zirconium dioxide (with the particle size of 100 nm) and 265.40g of tantalum oxide (with the particle size of 1 mu m) are weighed and mixed by a high-speed mixer at the rotating speed of 30000rpm for 30min to obtain a mixture A.
(2) And transferring the mixture into an isostatic pressing die, granulating under the pressure of 180MPa, and demolding to obtain a block. Crushing the block by a jaw crusher to obtain powder, and sieving by a 80-mesh sieve.
(3) Mixing the powder and 522.8g of lithium carbonate together by a high-speed mixer for 30min to obtain a mixture B, then keeping the temperature of the mixture B at 900 ℃ for 6h, and cooling to obtain a target material Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 。
The mixture a, the powder and the mixture B of the present example were characterized by using an electron microscope, and the results are shown in fig. 1-3 (in each figure, (B) is an enlarged view of (a)), as can be seen from fig. 1 (a) and (B), the mixture a simply mixed is obviously in a loose state, most of the powder particles are in a dispersed state, and the distance between the particles is large; as can be seen from fig. 2 (a) and (b), the crushed powder particles after granulation have edges and corners, and basically no loose powder is around the large particles, both indicating that the agglomerated particles are more compact; as can be seen from fig. 3 (a), in the mixture B, the micron-sized lithium carbonate particles are uniformly dispersed in the plurality of fine particles, and as can be seen from fig. 3 (B), the binding force between the plurality of fine powder particles in the mixture B is very tight. The electron microscope image shows that the sintered powder obtained by the scheme of the invention has better compactness and dispersion degree.
Example 2:
the preparation process of the multielement material of the embodiment comprises the following steps:
(1) 1006.73g of lanthanum oxide (with the particle size of 500 nm), 345.36g of zirconium dioxide (with the particle size of 500 nm) and 265.40g of tantalum oxide (with the particle size of 1 mu m) are weighed and mixed by a high-speed mixer at the rotating speed of 30000rpm for 30min to obtain a mixture A.
(2) And transferring the mixture into a cold pressing die, granulating under the pressure of 100MPa, demolding to obtain a block, crushing the block by using a jet mill to obtain powder, and screening by using a 100-mesh sieve.
(3) Mixing the powder with 522.8g of lithium oxalate continuously for 30min by using a high-speed mixer to obtain a mixture B, then preserving the temperature of the mixture B at 900 ℃ for 6h, and cooling to obtain a target material Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 。
Example 3:
the preparation process of the multielement material of the embodiment comprises the following steps:
(1) 373.55g of nickel oxide (particle size of 5 μm), 160.5.g of cobaltosic oxide (particle size of 500 nm) and 260.82g of manganese dioxide (particle size of 1 μm) were weighed and mixed by a high-speed mixer at 30000rpm for 30min to obtain a mixture A.
(2) Transferring the mixture into a cold pressing die, granulating under the pressure of 50MPa, demolding to obtain a block, crushing the block by using a jaw crusher to obtain powder, and sieving by using a 200-mesh sieve.
(3) Mixing the powder and 394.5 lithium carbonate together with high speed mixer for 30min to obtain mixture B, maintaining the temperature of the mixture B at 900 deg.C for 16h, and cooling to obtain target material Li (Ni) 0.5 Co 0.2 Mn 0.3 )O 2 。
Example 4:
the preparation process of the multielement material of the embodiment comprises the following steps:
(1) 373.55g of nickel oxide (particle size: 1 μm), 160.5 g of cobaltosic oxide (particle size: 800 nm) and 260.82g of manganese dioxide (particle size: 100 nm) were weighed and mixed by means of a twin-screw conical mixer at 30000rpm for 30min to obtain a mixed material A, which was then sieved through a 500-mesh sieve.
(2) And transferring the mixture into an isostatic pressing cavity, granulating under the pressure of 200MPa, demolding to obtain a block, and crushing the block by using a hammer crusher to obtain powder.
(3) Mixing the powder and 394.5g lithium acetate with a high-speed mixer for 30min to obtain a mixture B, keeping the temperature of the mixture B at 900 ℃ for 12h, and cooling to obtain a target material Li (Ni) 0.5 Co 0.2 Mn 0.3 )O 2 。
Comparative example 1:
the preparation process of the multielement material of the present comparative example comprises the following steps:
(1) 1006.73g of lanthanum oxide (with the particle size of 500 nm), 345.36g of zirconium dioxide (with the particle size of 100 nm), 265.40g of tantalum oxide (with the particle size of 1 mu m) and 750g of isopropanol are weighed and mixed for 360min at the rotating speed of 300rpm by a ball mill to obtain a mixture.
(2) And (3) drying the mixture at 100 ℃ by air blowing for 12 hours to obtain a dry material.
(3) Keeping the temperature of the dry material at 900 ℃ for 6h, and cooling to obtain the target material Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 。
Comparative example 2:
the preparation process of the multielement material of the present comparative example comprises the following steps:
(1) 1006.73g of lanthanum oxide (with the particle size of 500 nm), 345.36g of zirconium dioxide (with the particle size of 100 nm) and 265.40g of tantalum oxide (with the particle size of 1 μm) are weighed and mixed by a high-speed mixer at the rotating speed of 30000rpm for 30min to obtain a mixture.
(2) Mixing the mixture with 522.8g of lithium carbonate by a high-speed mixer for 30min, keeping the temperature at 900 ℃ for 6h, and cooling to obtain the target material Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 。
The phase of the final product is tested by using an X-ray spectrometer for example 1 and comparative examples 1 and 2, and compared by using PDF #40-0159 as a standard card, and the result is shown in FIG. 4, as can be seen from FIG. 4, the phase obtained by adopting the scheme is basically consistent with that obtained by adopting the traditional wet mixing scheme (comparative example 1); when the raw materials were simply mixed (comparative example 2), the amount of the impurity phase in the target material was very large, indicating that a large amount of impurity phase was present in the sintered product. The proposal of the invention is fully superior to simple high mixing material, and can achieve the same and basically consistent effect with the wet mixing material sintering process.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described examples. It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit of the invention.
Claims (6)
1. A preparation process of a multi-element material is characterized by comprising the following steps:
(1) Preparing required raw materials, wherein the raw materials comprise a lithium-containing raw material and other element raw materials; uniformly mixing other element raw materials to obtain a mixture, wherein no solvent is added in the mixing process of the other element raw materials;
(2) Granulating and crushing the mixture to obtain powder; the pressure of the granulation operation is 2 to 200MPa; the granularity D50 of the powder is 1 to 100 mu m, and the granularity D90 of the powder is 50 to 150 mu m;
(3) And uniformly mixing the powder with a lithium-containing raw material, and keeping the temperature of the mixture at 500 to 1200 ℃ for 2 to 1697 hours to obtain the multi-element material.
2. The process for preparing the multielement material according to claim 1, wherein the grain sizes of the lithium containing material and the other elemental materials are both 0.01-10 μm.
3. The process for the preparation of the multielement material according to claim 1, characterized in that the pelletizing operation in step (2) is a die or isostatic pelletizing process.
4. The process according to claim 1, wherein the raw material, lithium containing raw material or other elemental raw material is one or several of oxides, sulfides, phosphates, oxalates, carbonates, acetates, hydroxides and halides.
5. The process for the preparation of the multi-element material according to claim 1, wherein the mixing of the raw materials in step (1) is performed by one or more of a tilting cylinder mixer, a twin-screw conical mixer and a high-speed mixer.
6. The multi-element material manufacturing process of claim 1, wherein the crushing of the mix in step (2) is performed by one or more of a jaw crusher, a hammer crusher, a roll crusher, a jet mill, a high speed mixer and a mechanical crusher.
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2020
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Patent Citations (7)
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| CN101597048A (en) * | 2009-04-16 | 2009-12-09 | 丁建民 | A kind of preparation method of LiFePO 4 of anode material |
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