CN108649148B - Preparation method of barren aluminum titanate composite material sagger - Google Patents
Preparation method of barren aluminum titanate composite material sagger Download PDFInfo
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- CN108649148B CN108649148B CN201810638918.7A CN201810638918A CN108649148B CN 108649148 B CN108649148 B CN 108649148B CN 201810638918 A CN201810638918 A CN 201810638918A CN 108649148 B CN108649148 B CN 108649148B
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- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 title claims abstract description 89
- 229910000505 Al2TiO5 Inorganic materials 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 106
- 238000005469 granulation Methods 0.000 claims abstract description 31
- 230000003179 granulation Effects 0.000 claims abstract description 31
- 238000003825 pressing Methods 0.000 claims abstract description 27
- 238000000465 moulding Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 40
- 229910052744 lithium Inorganic materials 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 17
- 229910052661 anorthite Inorganic materials 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052878 cordierite Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 claims description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 10
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052637 diopside Inorganic materials 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 230000035939 shock Effects 0.000 description 11
- 239000003513 alkali Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- -1 lithium Nickel Cobalt Aluminum Chemical compound 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001597 celsian Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 210000001161 mammalian embryo Anatomy 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of barren aluminum titanate composite sagger, which comprises the following steps: (1) granulating barren aluminum titanate composite material powder to obtain granulated powder; (2) pressing and molding the obtained granulation powder to obtain a blank body; (3) and sintering the obtained blank to obtain the sagger.
Description
Technical Field
The invention relates to a manufacturing method and application of a sagger made of lean aluminum titanate composite material with super-strong corrosion resistance, in particular to a sagger special for a lithium battery.
Background
With the continuous deepening of the application of the lithium battery, the usage amount is increased year by year, and the lithium battery plays an important role in the world lithium battery production as a large lithium battery production country in China. Lithium batteries are various in types, and because of different anode materials, lithium batteries mainly comprise: lithium iron phosphate (LFP), Lithium Nickelate (LNO), Lithium Manganate (LMO), Lithium Cobaltate (LCO), ternary lithium Nickel Cobalt Manganese (NCM) and ternary lithium Nickel Cobalt Aluminum (NCA), wherein the negative electrode material mainly adopts a graphite carbon material. Among them, ternary lithium nickel cobalt manganese oxide (NCM) and ternary lithium Nickel Cobalt Aluminate (NCA) are becoming the development direction of future lithium batteries due to their high energy density and long cycle times. The lithium battery brings convenience to life, and the production process has the problem of energy consumption inevitably, wherein the problem is mainly embodied as solid phase reaction sintering at high temperature, in addition to the electricity consumption in the whole process, the other part of main consumption materials are a kiln and kiln furniture, and the sagger consumption directly contacting with the lithium battery raw material is taken as serious consumption. The most used anode materials of lithium batteries in the current market are cordierite-mullite-corundum saggars, which have the advantages of low expansion coefficient, good thermal shock property, low raw material cost, easy obtainment and the like, besides ternary lithium batteries, the saggars are used for sintering anode materials of common lithium batteries and have the service life of about 20 times, but if the saggars are used as containers for reaction sintering of the anode materials of the ternary lithium batteries, the service life of the saggars is about 10 times, and the main scrapping reasons are as follows: the ternary lithium battery raw material reacts with the refractory material to produce an erosion layer of a glass phase substance, the erosion layer has a large expansion coefficient, is poor in thermal shock property and easy to crack, and the expansion coefficient of the erosion layer is greatly different from that of the original sagger ligand, so that the erosion layer is easy to crack, fall and pollute the lithium battery raw material. The ternary lithium battery anode material contains nickel, and the scrapped saggars are used as industrial wastes and need to be treated as chemicals, so that the treatment cost is high, and secondary pollution is easily caused. The service life of the sagger for the ternary lithium battery is prolonged, and the sagger becomes one of the main pressures faced by the development of the ternary lithium battery at present. The average index of saggar consumption at home and abroad is 200-300 kg for each ton of anode material, which causes great pressure on the environment, and the development of a special saggar suitable for lithium battery sintering is imperative.
Through material analysis of lithium battery materials, the sagger for the lithium battery needs low expansion coefficient, good thermal shock resistance and alkali resistance, lithium in a common lithium battery is introduced in the form of lithium carbonate, the alkalinity is low, but lithium in a ternary lithium battery is introduced in the form of lithium hydroxide, the alkalinity is high, ceramic materials such as mullite and the like are generally acid-resistant and alkali-resistant, and particularly, the materials are greatly corroded by alkali at high temperature. One ceramic material that has very excellent performance in terms of alkali resistance is aluminum titanate. The aluminum titanate mainly takes ionic bonds and covalent bonds as bonding bonds, and has crystal phases and air holes inside from the aspect of microstructure and state, which determines that the aluminum titanate has the advantages of low heat conductivity, slag resistance, alkali resistance, corrosion resistance and non-wettability to various metals and glass, which are not possessed by metal materials and high polymer materials, so that the aluminum titanate has wide application under harsh conditions such as wear resistance, high temperature resistance, alkali resistance, corrosion resistance and the like, and particularly has the lowest expansion coefficient in known ceramic materials when high thermal shock resistance is required. Meanwhile, aluminum titanate is easy to decompose at about 1100 ℃, has the defects of low mechanical strength and the like, so that pure aluminum titanate is difficult to obtain at normal temperature, the mechanical strength is low, the practical utilization value is lacked, stable aluminum titanate with good mechanical strength generally exists in the form of composite materials, the aluminum titanate composite materials not only have the advantages of the aluminum titanate, but also avoid the defects of the aluminum titanate composite materials, and the aluminum titanate composite materials are undoubtedly raw materials which are very suitable for sagger used in the lithium battery industry. However, the aluminum titanate composite material is a poor raw material and has no plasticity.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for producing a sagger made of barren aluminum titanate composite material.
Provided herein is a method for preparing a barren aluminum titanate composite sagger, comprising the steps of:
(1) granulating barren aluminum titanate composite material powder to obtain granulated powder;
(2) pressing and molding the obtained granulation powder to obtain a blank body;
(3) and sintering the obtained blank to obtain the sagger.
According to the present invention, the barren aluminum titanate composite material can be formed into a saggar having a specific size by granulation and then compression molding.
The barren aluminum titanate composite may be selected from the group consisting of anorthite cordierite composites.
Preferably, step (1) comprises:
mixing and ball-milling barren aluminum titanate composite material powder, polyvinyl alcohol solution which accounts for 2-10% of the weight of the barren aluminum titanate composite material powder, 40-100% of water, 0.1-0.5% of sodium tripolyphosphate and 0.01-0.1% of n-octanol to obtain slurry; and
and (4) carrying out spray granulation on the obtained slurry to obtain granulated powder.
According to the present invention, a powder slurry of an aluminum titanate composite material having a high solid content and stable dispersion can be obtained, and further granulated powder suitable for dry-pressing can be obtained.
Preferably, the particle size of the barren aluminum titanate composite powder is 325 mesh or more.
Preferably, the moisture content of the obtained granulated powder is controlled to be 0.1-1%, and the particle size is 10-200 um, preferably 50-150 um.
Preferably, in the step (2), the pressing pressure is 8 to 20 MPa.
Preferably, in the step (1), the barren aluminum titanate composite aggregate and the barren aluminum titanate composite powder having a particle diameter of 0.1mm to 1mm in a weight ratio of 1:2 to 1:1 are granulated with 0.5 to 1% of carboxymethyl cellulose, 1 to 2% of a potassium laurate solution, and 3 to 10% of water based on the weight of the mixture of the aggregate and the powder.
According to the invention, granulated powder suitable for semi-dry pressing molding can be obtained.
Preferably, step (1) comprises:
mixing the barren aluminum titanate composite material powder and the carboxymethyl cellulose to obtain mixed powder;
mixing the potassium laurate solution with the water to obtain a mixed liquid; and
and (2) putting the barren aluminum titanate composite aggregate into crushing equipment for crushing, adding part of the mixed liquid in the crushing process, adding the mixed powder after the moisture in the aggregate is uniform, uniformly adding the rest of the mixed liquid until the powder in the crushing equipment is in a sand granule shape, and finishing granulation.
Preferably, the crushing apparatus is an edge runner mill.
Preferably, in the step (2), the pressing pressure is 8 to 20 MPa.
According to the invention, the aluminum titanate composite material sagger with low expansion rate, good thermal shock property and strong alkali resistance can be obtained by a simple method.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are to be understood as merely illustrative, and not restrictive, of the invention. In this specification, all percentages are by weight unless otherwise indicated.
Disclosed herein is a method for preparing an aluminum titanate composite sagger.
In the present disclosure, an "aluminum titanate composite sagger" refers to a sagger made of aluminum titanate composite. "sagger" refers to a container for firing. The "aluminum titanate composite material" refers to a material obtained by compounding aluminum titanate with other components, and includes a synthesized aluminum titanate composite material, a formulation (raw material) for synthesizing an aluminum titanate composite material upon calcination, and the like. In the present disclosure, the aluminum titanate composite material is not particularly limited, but mainly aims at a barren aluminum titanate composite material. The poor property means that the ceramic powder after firing or the raw material obtained after firing has no stickiness after mixing with water. As specific examples of barren aluminum titanate composites, for example, anorthite cordierite composites, and formulations of anorthite cordierite composites are disclosed.
The anorthite-cordierite composite material contains aluminium titanate and anorthite CaO-Al2O3·2SiO2And cordierite Mg2Al4Si5O18The composite phase of (1). In a preferred embodiment, the content of aluminum titanate in the anorthite cordierite composite material is 60 to 80% by mass, and anorthite CaO · Al is2O3·2SiO210-20% of cordierite Mg2Al4Si5O18The content of (A) is 10-20%.
In one example, the formulation of the anorthite cordierite composite material comprises alumina powder, titania powder, and diopside powder, which are barren materials. In a preferred embodiment, the weight percentages of the raw materials are as follows: 40-55% of alumina powder, 25-35% of titanium dioxide powder and 15-35% of diopside powder.
In addition, the sagger in the present disclosure is preferably a sagger for lithium battery, specifically, a sagger for sintering a lithium battery positive electrode material, and is preferably a sagger for sintering a ternary lithium battery positive electrode material. Examples of the positive electrode material of the ternary lithium battery include nickel cobalt manganese ternary lithium (NCM), nickel cobalt aluminum ternary lithium (NCA), and the like.
The production process of the aluminum titanate composite material sagger can comprise forming, drying, sintering and the like.
In one embodiment, the production molding is performed in a dry pressing manner. The molding step is described in detail below.
Firstly, ball milling is carried out on aluminum titanate composite material powder and an additive to obtain slurry. Here, the "aluminum titanate composite powder" may be a synthesized aluminum titanate composite powder or a formulated material powder for synthesizing an aluminum titanate composite.
The particle size of the aluminum titanate composite material powder can be more than 325 meshes, so that a more compact blank can be obtained, the porosity of gas is reduced, and sintering is promoted. More preferably, the particle size of the aluminum titanate composite material powder is 800 to 1250 mesh.
The additives may include a polyvinyl alcohol solution as a binder, water (preferably purified water) as a dispersion medium, sodium tripolyphosphate as a water reducing agent, and n-octanol as a defoaming agent.
The concentration of the polyvinyl alcohol solution may be 5 to 15%, for example 10%. The amount of the polyvinyl alcohol solution added may be 2 to 10% by weight, more preferably 5 to 10% by weight, based on the weight of the powder. Therefore, the mechanical strength of the pressed blank can be improved, and the loss of organic matters in the sintering process can be effectively controlled.
The amount of water added may be 40 to 100% by weight, more preferably 50 to 60% by weight, based on the weight of the powder. Therefore, the fluidity of the slurry can be ensured, and the granulation powder with better compactness can be obtained.
The addition amount of the sodium tripolyphosphate can be 0.1-0.5% of the weight of the powder, and more preferably 0.1-0.2%. Therefore, the slurry with higher solid content can be obtained, and the slurry with good fluidity can be obtained under the condition of adding 50 percent of purified water.
The addition amount of n-octanol may be 0.01% to 0.1%, more preferably 0.02% of the weight of the powder. Therefore, no foam is generated on the surface of the slurry after ball milling, and no foam is generated in the material pouring process.
The ball milling time may be 30 to 60 minutes, for example, about 30 minutes.
And granulating the obtained slurry, preferably performing spray granulation by using a ceramic spray granulation device to obtain granulated powder. The water content of the granulated powder can be controlled between 0.1% and 1%, and more preferably 0.5% to 1%. Therefore, under the condition of the same pressure in the pressing process, the embryo body with better strength can be obtained. The grain size of the granulated powder can be controlled between 10-200 um, and more preferably between 50-150 um. Therefore, the flowability of the granulated powder can be increased, the discharge of internal gas in the pressing process is facilitated, and the internal defects are reduced.
And pressing and molding the granulation powder to obtain a sagger blank. The pressing pressure can be 8-20 MPa. In one example, the granulated powder is charged into a special sagger mold installed in a large-tonnage press, and the granulated powder is pressed into a sagger blank with a certain mechanical strength by using the pressure of the large-tonnage press.
The product is compact and has smooth surface by adopting a dry pressing forming process.
In one embodiment, the production molding is performed in a semi-dry pressing manner. The molding step is described in detail below.
First, an aluminum titanate composite aggregate and an aluminum titanate composite powder are granulated together with an additive. Here, the "aluminum titanate composite aggregate" may be a synthesized aluminum titanate composite aggregate, or may be a formulation aggregate for synthesizing an aluminum titanate composite. The "aluminum titanate composite powder" may be a synthesized aluminum titanate composite powder or a formulated material powder for synthesizing an aluminum titanate composite.
The aluminum titanate composite aggregate is a granular material with the particle size of more than 0.1mm, and can be obtained by crushing, grinding and sieving. The particle diameter of the aluminum titanate composite ceramic aggregate is preferably 0.1mm to 1 mm.
The particle size of the aluminum titanate composite material powder can be 325-800 meshes.
The aluminum titanate composite aggregate and the aluminum titanate composite powder are granulated together, so that the problem of high energy consumption caused by spray granulation can be avoided.
The weight ratio of the aluminum titanate composite aggregate to the aluminum titanate composite powder can be 1: 2-1: 1, so that granulated powder with better particle size can be obtained.
The additives may include carboxymethyl cellulose (CMC) as a binder, potassium laurate as a forming lubricant, and water (preferably purified water) as a dispersion medium.
The amount of the carboxymethyl cellulose added may be 0.5 to 1% of the weight of the mixture of the aluminum titanate composite ceramic aggregate and the aluminum titanate ceramic composite powder (hereinafter referred to as the mixed weight). Therefore, the problem that the barren material has no viscosity in the pressing process can be solved, and the powder bodies are bonded together through high pressure to obtain the embryo body meeting the strength requirement.
The potassium laurate may be added in the form of an aqueous solution, the concentration of which may be 30 to 40%, for example 30%. The addition amount of the potassium laurate aqueous solution can be 1 to 2 percent of the mixing weight. Therefore, the lubricating property of the barren material can be increased, the fluidity of the pug can be improved, and the granulated powder is beneficial to compression molding.
The amount of water added may be 4 to 12% of the weight of the mixture. The pug properties were adjusted to be suitable for pressing saggars.
In one example, aluminum titanate composite powder and carboxymethyl cellulose (CMC) are thoroughly mixed to obtain a mixed powder. And uniformly mixing the potassium laurate solution and water to obtain a mixed liquid.
The device used for granulation is preferably an edge runner mill, so that the aggregate and the powder can be formed into small granules which take the aggregate as a core and are wrapped by the powder by repeated edge runner milling, and the granulation is commonly called as granulation.
Putting the aluminum titanate composite ceramic aggregate into an edge runner mill, starting the edge runner mill, adding a part of mixed liquid in a proper amount, adding a mixed powder part after the moisture in the aggregate is basically uniform, slowly and uniformly adding the rest of mixed liquid until the powder in the edge runner mill is in a sand granule shape, and finishing granulation.
The obtained granulated powder has a water content of 3 to 10% and a particle diameter of 0.2 to 3 mm.
And pressing and molding the granulation powder to obtain a sagger blank. The pressing pressure can be 8-20 MPa. In one example, the granulated powder is charged into a special sagger mold installed in a large-tonnage press, and the granulated powder is pressed into a sagger blank with a certain mechanical strength by using the pressure of the large-tonnage press.
The semi-dry pressing forming process has the advantages of simple process and low production cost.
The obtained sagger blank can be dried and sintered to obtain the sagger. The sintering temperature can be different according to different aluminum titanate composite materials, and generally can be 1450-1550 ℃.
In the disclosure, the prepared aluminum titanate composite material sagger has low expansion rate, good thermal shock property and strong alkali resistance. For example, the thermal shock resistance is 650-800 ℃ for three times without cracking, the thermal expansion coefficient is 0.5-1.2 multiplied by 10E < -6 >, and the sagger is particularly suitable for being used as a special sagger for lithium batteries.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
EXAMPLE 1 Dry Press Molding
In this embodiment, the aluminum titanate composite material is a formula material of the celsian diopside titanate, which includes 50% of alumina powder, 35% of titanium dioxide powder, and 15% of diopside powder.
1. Ball milling: adding 10% PVA solution with the weight of 10% of powder, 50% purified water, 0.2% sodium tripolyphosphate as a water reducing agent and 0.01% n-octyl alcohol as a defoaming agent into aluminum titanate composite material formula powder with the particle size of 1250 meshes above, adding the mixture into a ball mill, and ball-milling for about 30 minutes to obtain powder slurry of the aluminum titanate composite material formula material with high solid content, uniform dispersion and stability.
2. And (3) granulation: and carrying out spray granulation on the powder slurry of the aluminum titanate composite material formula material obtained by ball milling by using ceramic spray granulation equipment, wherein the water content of the powder is controlled to be 0.5-1%, and the particle size of the granulated powder is 50-150 um.
3. Dry pressing: the aluminum titanate composite material granulation powder is quantitatively added into a special sagger mold arranged in a large-tonnage press, and the granulation powder is pressed into a sagger blank with certain mechanical strength by utilizing the pressure (15MPa) of the large-tonnage press.
4. Drying and sintering: and drying the sagger blank at 120 ℃ for 4 hours, and then sintering and preserving heat at 1550 ℃ for 6 hours to obtain the sagger.
EXAMPLE 2 semi-dry Press Molding
In this embodiment, the aluminum titanate composite material is a formula material of the celsian diopside titanate, which includes 50% of alumina powder, 35% of titanium dioxide powder, and 15% of diopside powder.
1. Preparation of materials: the weight ratio of the formula aggregate with the particle diameter of 0.1-0.7mm to the formula powder with the particle diameter of 325-800 meshes is 40:60, 1 percent of carboxymethyl cellulose (CMC) is used as a binder by the mixed weight of the formula aggregate and the formula powder, 30 percent of potassium laurate with the mixed weight of 2 percent is used as a forming lubricant, and 6 percent of purified water by the mixed weight is used.
2. And (3) granulation: the preparation method comprises the steps of fully mixing formula material powder and carboxymethyl cellulose (CMC) in advance, uniformly mixing a potassium laurate solution and purified water, and granulating by using an edge runner mill, wherein formula material aggregate is firstly put into the edge runner mill, the edge runner mill is started, a proper amount of partial liquid is added, after the moisture in the formula material aggregate is basically uniform, the powder part is added, the residual liquid is slowly and uniformly added until the powder in the edge runner mill is in a sand-like shape, and the granulation is finished. The water content of the powder is 5 percent, and the grain diameter of the granulated powder is between 0.5 and 2 mm.
3. Semi-dry pressing: the granulation powder consisting of the aggregate of the formula material and the powder of the formula material is quantitatively added into a special sagger die arranged in a large-tonnage press, and the pressure (18MPa) of the large-tonnage press is utilized to press the granulation powder into a sagger blank with certain mechanical strength.
4. Drying and sintering: the sagger body is naturally dried in the shade for 2 days, dried at 120 ℃ for 4 hours and then sintered at 1550 ℃ for 6 hours to obtain the sagger.
Performance testing
And testing the expansion rate of the obtained sagger by adopting a thermal expansion coefficient tester method, testing the thermal shock property of the obtained sagger by adopting a method of directly placing the sagger into an electric furnace at the room temperature of 650 ℃ or 800 ℃ for heat preservation for 30 minutes and then taking the sagger out to the room temperature environment for natural cooling, and testing the alkali resistance of the obtained sagger by adopting a method of putting the sagger into the production of the high-nickel ternary lithium battery.
The sagger of the anorthite cordierite composite material obtained by the spray granulation and dry pressing process (example 1) has the expansion coefficient of about 0.5 multiplied by 10E < -6 > and the thermal shock property of three times of 800 ℃ without cracking, is used in the sagger of the high-nickel ternary lithium battery with the strongest corrosivity at present, has the use frequency of about 40 times, has the best performance in the market at present and comprises an imported sagger. The sagger of the anorthite cordierite composite material obtained by the process of granulation by a wheel mill and semi-dry pressure granulation (example 2) has the expansion coefficient of about 1.5 multiplied by 10E < -6 > and thermal shock property of no cracking at three times of 600 ℃, is used as the sagger of the high-nickel ternary lithium battery with the strongest corrosivity at present, has the use frequency of about 25 times, and has the service life basically similar to that of the sagger imported in the current market.
The sagger obtained by adopting the spray granulation and dry pressing process has better compactness and consistency, can obtain a product with a lower expansion coefficient, has better thermal shock performance, and has better corrosion resistance due to good compactness, lower porosity. The sagger obtained by the process of granulating by using the edge runner mill and granulating by using the semi-dry pressure is simpler in process and lower in production cost.
Claims (5)
1. A preparation method of a barren aluminum titanate composite material sagger for sintering a ternary lithium battery anode material is characterized in that the barren aluminum titanate composite material is an anorthite cordierite composite material; in the anorthite cordierite composite material, the content of aluminum titanate is 60-80% by mass, and anorthite CaO & Al2O3·2SiO210-20% of cordierite Mg2Al4Si5O18The content of (A) is 10-20%; the formula material of the anorthite cordierite composite material comprises alumina powder, titanium dioxide powder and diopside powder; wherein the weight percentages of the raw materials are as follows: 40-55% of alumina powder, 25-35% of titanium dioxide powder and 15-35% of diopside powder;
the preparation method comprises the following steps:
(1) granulating barren aluminum titanate composite material powder to obtain granulated powder; pressing and molding the obtained granulation powder to obtain a blank body;
when the molding is dry pressing, mixing and ball-milling the barren aluminum titanate composite material powder, a polyvinyl alcohol solution accounting for 2-10% of the weight of the barren aluminum titanate composite material powder, 40-100% of water, 0.1-0.5% of sodium tripolyphosphate and 0.01-0.1% of n-octanol to obtain slurry; and spray granulating the obtained slurry to obtain granulated powder;
when the molding is semi-dry pressing molding, granulating barren aluminum titanate composite material aggregate and barren aluminum titanate composite material powder in a weight ratio of 1: 2-1: 1, and 0.5-1% of carboxymethyl cellulose, 1-2% of potassium laurate solution and 3-10% of water relative to the mixed weight of the barren aluminum titanate composite material aggregate and the barren aluminum titanate composite material powder to obtain granulated powder;
(2) and sintering the obtained blank to obtain the sagger.
2. The method according to claim 1, wherein the barren aluminum titanate composite powder has a particle size of 325 mesh or more when the molding is dry-pressed.
3. The method according to claim 1, wherein when the molding is dry-pressing, the moisture content of the obtained granulated powder is controlled to be 0.1-1%, and the particle size is 10-200 μm; when the molding is a semi-dry molding, the obtained granulated powder has a water content of 3-10% and a particle size of 0.2-3 mm.
4. The method according to claim 1, wherein in the step (1), the pressing pressure is 8 to 20 MPa.
5. The manufacturing method as set forth in claim 1, wherein when the molding is a semi-dry press molding, the step (1) includes:
mixing the barren aluminum titanate composite material powder and the carboxymethyl cellulose to obtain mixed powder;
mixing the potassium laurate solution with the water to obtain a mixed liquid; and
and putting the barren aluminum titanate composite material aggregate into an edge runner mill device for edge runner milling granulation, adding part of the mixed liquid in the edge runner mill process, adding the mixed powder after the moisture in the aggregate is uniform, uniformly adding the rest of the mixed liquid until the powder in the edge runner mill device is in a sand-like shape, and finishing granulation.
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