CN117613276A - Porous inorganic material for battery, preparation method thereof and battery - Google Patents
Porous inorganic material for battery, preparation method thereof and battery Download PDFInfo
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- CN117613276A CN117613276A CN202311642317.0A CN202311642317A CN117613276A CN 117613276 A CN117613276 A CN 117613276A CN 202311642317 A CN202311642317 A CN 202311642317A CN 117613276 A CN117613276 A CN 117613276A
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- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 31
- 239000011147 inorganic material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005530 etching Methods 0.000 claims abstract description 49
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010457 zeolite Substances 0.000 claims abstract description 37
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 13
- -1 aluminosilicate compound Chemical class 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000006183 anode active material Substances 0.000 claims abstract description 5
- 239000006182 cathode active material Substances 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000010306 acid treatment Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 229910052611 pyroxene Inorganic materials 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 239000010954 inorganic particle Substances 0.000 description 19
- 239000012528 membrane Substances 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000002808 molecular sieve Substances 0.000 description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention provides a porous inorganic material for a battery, a preparation method thereof and the battery, wherein the preparation method comprises the following steps: providing a raw material, wherein the raw material is any one or more of zeolite and aluminosilicate compound; and etching the raw materials to obtain the porous inorganic material for the battery. According to the preparation method provided by the embodiment of the invention, the zeolite and aluminosilicate compound serving as raw materials are etched to obtain the three-dimensional porous structure, and the three-dimensional porous structure is formed by etching, so that on one hand, the contact area between the zeolite and electrolyte is increased, the addition of the zeolite and aluminosilicate compound does not cause obvious increase of the internal resistance of the battery, and on the other hand, the zeolite and aluminosilicate compound are added into the diaphragm, so that the thermal stability and wettability of the diaphragm are improved, and the cycle performance of the battery is improved, and the stability and the service life of the zeolite and aluminosilicate compound can be improved when the zeolite and aluminosilicate compound are applied to an anode active material layer and a cathode active material layer.
Description
Technical Field
The invention relates to the technical field of battery preparation, in particular to a porous inorganic material for a battery, a preparation method thereof and the battery.
Background
With the development of new energy sources and electric vehicles, electrochemical cells as energy storage devices play an increasingly important role in socioeconomic and life. Therefore, high performance electrochemical cells will be an important driving force for new energy sources and electric vehicles.
The main causes of low electrochemical cell performance include: conventional organic separators have low thermal stability and low wettability. The low thermal stability causes the condensation polymerization of the organic polymer membrane at high temperature, causes the short circuit of the anode and the cathode, even causes thermal runaway, and simultaneously the low wettability causes the mass transfer resistance of the load ions to be increased, thereby reducing the rate capability of the battery.
There is a study to improve the above problems by adding an inert inorganic material to a positive electrode active material, a negative electrode active material, and a separator of a battery, respectively.
However, it was found that the addition of inert inorganic materials to the battery tends to affect the internal resistance of the battery and easily results in a decrease in the energy density of the battery.
Disclosure of Invention
The inventor has repeatedly studied and found that natural or synthetic inorganic materials tend to have compact structures and high densities, and when the inorganic materials are added into a battery, only the surfaces of inorganic material particles act, and electrolyte cannot penetrate into the particles to act. Therefore, on one hand, the load ion conduction capacity is obviously reduced, the overall internal resistance of the battery is increased, the rate performance of the device is not facilitated, and on the other hand, the energy density of the battery is reduced. Although it is possible to achieve the same effect by grinding inorganic particles, the grinding of the particles not only increases the cost, but also causes difficulty in use and storage due to agglomeration of the particles.
On the other hand, the inventor has found that by etching the inorganic particles to form a three-dimensional porous structure, the density of the inorganic particles can be reduced, and the liquid absorbing capacity of the inorganic particles and the adsorption capacity of the inorganic particles to harmful transition metal elements can be increased, so that the problems of residual moisture influence, crosstalk, thermal stability and the like can be solved, and the device has better performance in terms of the rate performance of the device and the energy density of the battery, thereby enhancing the improvement effect on the chemical performance of the battery.
The present inventors have made repeated studies and experiments on the basis of the above-described study, and completed the present invention.
The invention aims to provide a porous inorganic material for a battery, a preparation method thereof and the battery, wherein the porous inorganic material can have the processing cost and the comprehensive electrical property when the porous inorganic material is used for the battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a porous inorganic material for a battery according to an embodiment of the first aspect of the present invention includes:
providing a raw material, wherein the raw material is any one or more of zeolite and aluminosilicate compound;
and etching the raw materials to obtain the porous inorganic material for the battery.
Further, the zeolite is an 8-membered ring, a 9-membered ring, a 10-membered ring, a 12-membered ring, or a mixture thereof formed from silicon oxygen tetrahedra and TO4 through shared oxygen bridging, wherein T represents one or more of Al, B, P, fe, ti, W, ge, sn.
Further, the aluminosilicate compound includes any one or more of pyroxene, kaolin, talc, mica, montmorillonite, silica, feldspar.
Further, the etching treatment includes any one of an acid treatment and an alkali treatment.
Further, the acid in the acid treatment is selected from any one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, hydrofluoric acid and perchloric acid.
Further, the concentration of acid in the acid solution used in the acid treatment is 0.01mol/L-10mol/L, the treatment temperature is-10 ℃ to 200 ℃, and the treatment time is 1min-4d. Preferably, the acid is hydrochloric acid, the concentration of the hydrochloric acid is between 0.02mol/L and 1mol/L, the treatment temperature is between 25 and 100 ℃, and the treatment time is between 0.5 and 2 hours.
Further, the alkali used for the alkali treatment is selected from any one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, strontium hydroxide, ammonia water, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
Further, the concentration of alkali in the alkali solution used in the alkali treatment is between 0.01mol/L and 1mol/L, the treatment temperature is between-10 ℃ and 200 ℃, and the treatment time is between 1min and 4d. Preferably, the alkali is sodium hydroxide, the concentration of the sodium hydroxide is between 1mol/L and 1mol/L, the treatment temperature is between 25 and 100 ℃, and the treatment time is between 0.5 and 2 hours.
The porous inorganic material for a battery according to an embodiment of the second aspect of the present invention is prepared by the preparation method of any one of the embodiments of the first aspect.
A battery according to an embodiment of the third aspect of the present invention includes an electrolyte, a separator, an anode active material layer, and a cathode active material layer, any one or more of which contains the porous inorganic material for a battery according to the embodiment of the second aspect of the present application.
The technical scheme of the invention has at least one of the following beneficial effects:
according to the porous inorganic material for the battery, disclosed by the embodiment of the invention, the zeolite and the aluminosilicate compound serving as raw materials are etched to form a three-dimensional porous structure through etching, so that on one hand, the contact area between the porous inorganic material and electrolyte is increased, the addition of the porous inorganic material does not cause obvious increase of the internal resistance of the battery, and on the other hand, the porous inorganic material is added into a diaphragm, so that the thermal stability and wettability of the diaphragm are improved, and the cycle performance of the battery is improved, and the stability and the service life of the porous inorganic material can be improved when the porous inorganic material is applied to an anode active material layer and a cathode active material layer.
Drawings
FIG. 1 shows the XRD patterns of the porous inorganic material for batteries obtained in example 1;
FIG. 2 shows a graph of specific capacity as a function of cycle number for the separator obtained in example 2 versus the separator of comparative example 1;
fig. 3 shows the ac impedance spectra of different diaphragms.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which are obtained by a person skilled in the art based on the described embodiments of the invention, fall within the scope of protection of the invention.
First, the preparation method according to the present application is described in detail.
The preparation method of the porous inorganic material for the battery according to the embodiment of the invention comprises the following steps:
step S1: providing a raw material, wherein the raw material is any one or more of zeolite and aluminosilicate compound.
Wherein, as zeolite, for example, there may be mentioned an 8-membered ring, a 9-membered ring, a 10-membered ring, a 12-membered ring, or a mixture thereof formed by bridging a silicon oxygen tetrahedron and TO4 through a common oxygen, wherein T represents one or more of Al, B, P, fe, ti, W, ge, sn. Among them, zeolite is preferably one or more of FAU, MFI, MEL, MOR. These zeolites have developed microporous systems and dense structures, which allow for low electrolyte absorption and high density. The developed three-dimensional pore structure is constructed by etching to provide more specific surface area, so that the zeolite is more fully contacted with the electrolyte, and the weight ratio in the battery is reduced.
Further, the aluminosilicate compound may include any one or more of pyroxene, kaolin, talc, mica, montmorillonite, silica, feldspar.
Step S2: and etching the raw materials to obtain the porous inorganic material for the battery.
The etching treatment may include any one of acid treatment and alkali treatment. Of course, various treatments may be combined, for example, acid treatment followed by alkali treatment, and the like.
In order to achieve good results in battery applications, it is critical that the inorganic particles be etched to create as many three-dimensional channels as possible while maintaining a sufficient crystal structure. The three-dimensional pore canal junction has larger outer surface area, so that the inorganic particles are more fully contacted with the electrolyte.
The inorganic particles can be etched by the acid and the alkali, and the inorganic particles with ideal pore structures can be obtained by controlling etching conditions.
The concentration of the etchant, the etching temperature and the etching time are the most obvious factors influencing the etching effect. The etching agent concentration is too short or too short, the etching temperature is too low or too high, and the etching time is too short or too short, so that the best effect is not achieved. The etching effect is not obvious due to the fact that the concentration of the etching agent is too low, the etching temperature is too low and the etching time is too short, and enough pore channel structures cannot be formed; conversely, the excessive etching can be caused by the excessive concentration of the etchant, the excessive etching temperature and the excessive etching time, so that the effective external surface area is not reversely reduced, and even the crystal structure is damaged, thereby reducing the liquid absorption rate.
For the MFI zeolite molecular sieve, acid etching and alkali etching were performed using different concentrations, etching temperatures, and etching temperatures, respectively, and the electrolyte absorption rate of the zeolite particles after etching, the surface density of the resulting coated membrane, and the battery cycle performance were measured, and the results are shown in table 1 below.
Wherein, a coated separator is prepared: and coating the inorganic particles after etching treatment on the surface of the PE or PP base film. Firstly, inorganic particles, a dispersing agent (CMC), a binder (SBR) and deionized water are mixed according to the mass ratio of 20:2:1:67, mixing to prepare slurry, coating the slurry on a PE or PP base film, drying to remove water, and shearing the slurry into a required shape to obtain the etched MFI zeolite molecular sieve coating film.
Liquid absorption analysis: the inorganic particles obtained in the example 1 with a certain mass are weighed, added into electrolyte (1 mol/L LiPF6 in EC: DMC: EMC=1:1:1) for soaking for 1h, and inorganic particle powder is collected by suction filtration and weighed. The liquid absorption rate of inorganic particles is calculated by calculating the mass increase of inorganic ions before and after the electrolyte is infiltrated
Test of battery cycle performance: electrochemical performance of the coated separator was evaluated using 2016 buckling, 622 for positive electrode and lithium metal for negative electrode. Active material of positive electrode sheet: and (2) a binder: conductive agent=95:3:2.
TABLE 1 Performance test results obtained under different conditions
The results in table 1 show that the cell cycle life is positively correlated with the imbibition rate of the MFI zeolite molecular sieve after etching, i.e., the higher the imbibition rate, the better the cell cycle life. The liquid absorption rate of the MFI zeolite molecular sieve after etching is increased along with the increase of the concentration of the etchant (HCl and NaOH), the increase of the etching temperature and the increase of the etching time are firstly increased and then reduced, the optimal etching temperature is reached to 50 ℃ and the optimal etching time is about 0.5h when the concentration of the HCl is 0.1 and M, naOH is 0.4M.
Wherein the acid in the acid treatment is selected from any one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, hydrofluoric acid and perchloric acid. In addition, the acid concentration in the acid solution used for acid treatment is between 0.01mol/L and 10mol/L, the treatment temperature is between-10 ℃ and 200 ℃, and the treatment time is between 1min and 4d. Preferably, the acid is hydrochloric acid, the concentration of the hydrochloric acid is between 0.02mol/L and 1mol/L, the treatment temperature is between 25 and 100 ℃, and the treatment time is between 0.5 and 2 hours.
Further, the alkali used in the alkali treatment is selected from any one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, strontium hydroxide, ammonia water, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, the concentration of the alkali in the alkali solution used in the alkali treatment is between 0.01mol/L and 1mol/L, the treatment temperature is between-10 ℃ and 200 ℃, and the treatment time is between 1min and 4d. Preferably, the alkali is sodium hydroxide, the concentration of the sodium hydroxide is between 1mol/L and 1mol/L, the treatment temperature is between 25 and 100 ℃, and the treatment time is between 0.5 and 2 hours.
The preparation method according to the present application, and the porous inorganic material and battery prepared therefrom are further described in detail below in connection with specific examples.
It should be emphasized that the materials are exemplified here by zeolite only, and that corresponding experiments have been carried out by the inventors for other materials, which are omitted here.
Example 1: etching of zeolite
Mixing the MFI zeolite molecular sieve powder with 0.4mol/L NaOH solution, stirring for 1h at 50 ℃, washing with deionized water to neutrality, and drying for later use.
(1) XRD analysis and BET analysis results
As shown in figure 1, the etched molecular sieve powder has strong XRD characteristic diffraction peaks, which indicates that the crystal structure is complete.
However, BET experimental results showed that the mesoporous volume density was significantly increased (from 0.08cm3/g to 0.19cm3/g before etching).
(2) Liquid absorption analysis results
The absorption capacity of the inorganic particles into the electrolyte was evaluated by the liquid absorption rate. The specific analysis method is referred to above and will not be described here again.
The MFI zeolite molecular sieve powder obtained after etching in example 1 had a liquid absorption of 177%, whereas the unetched MFI molecular sieve powder had a liquid absorption of 120%.
Therefore, the liquid absorption rate is greatly improved after the etching treatment method is adopted.
Example 2 preparation of etched inorganic particle coated separator
The inorganic particles obtained in example 1 were coated on the surface of a PE or PP base film. Firstly, inorganic particles, a dispersing agent (CMC), a binder (SBR) and deionized water are mixed according to the mass ratio of 20:2:1:67, mixing to prepare slurry, coating the slurry on a PE or PP base film, drying to remove water, and shearing the slurry into a required shape to obtain the etched MFI zeolite molecular sieve coating film.
Comparative example 1
In contrast, the MFI zeolite molecular sieve coated membrane was prepared using exactly the same process, but without etching the inorganic particles.
Evaluation of Performance
(1) Areal density of
The areal density of the film ((m-coated membrane-m-base membrane)/film area) was calculated from the difference in film weights before and after coating and the film area. The surface density of the prepared MFI zeolite molecular sieve coating film is 5.12g/m2, and the surface density of the etched MFI zeolite molecular sieve coating film is 2.1g/m2, and the weight is reduced by 55%.
(2) Cycle performance
The circulation performance of the MFI zeolite coating film after etching is obviously better than that of the coating film before etching. Specifically, fig. 2 shows the cycle performance of a battery produced using different separators (MFI zeolite coated membrane before etching, i.e., the coated membrane produced in comparative example 1), and MFI zeolite coated membrane after etching, i.e., the coated membrane produced in example 1). As can be seen from fig. 2, the separator prepared by the method of the present invention has a cycle performance far superior to that of an untreated separator when used in a battery, and the cycle times are significantly reduced from the specific capacity of 200 times or more.
(3) AC impedance
In addition, the CHI electrochemical workstation was also used to test ac impedance. The 2016 button using stainless steel plate/diaphragm/stainless steel plate. The results are shown in fig. 3, where the ac impedance spectrum using a commercial PE separator is also shown as a comparison. As can be seen from fig. 3, the impedance of the MFI zeolite coated membrane before etching (comparative example 1 membrane), the MFI zeolite coated membrane after etching (example 2 membrane), and the commercial PE membrane were 5.2Ω, 4.4Ω, and 4.2Ω, respectively. Therefore, the impedance of the unetched MFI zeolite coated membrane is obviously higher than that of a commercial PE membrane, and the impedance of the etched MFI zeolite coated membrane is slightly higher than that of the commercial PE membrane, so that on one hand, the unetched bulk molecular sieve has poor absorption rate but poor ion transmission; on the other hand, the zeolite molecular sieve after simple etching treatment can improve the liquid absorption rate without greatly obstructing the ion transmission.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a porous inorganic material for a battery, comprising:
providing a raw material, wherein the raw material is any one or more of zeolite and aluminosilicate compound;
and etching the raw materials to obtain the porous inorganic material for the battery.
2. The method according to claim 1, wherein,
the zeolite is formed from silicon oxygen tetrahedra and TO4 through a common oxygen bridge TO form an 8-membered ring, a 9-membered ring, a 10-membered ring, a 12-membered ring, or mixtures thereof, wherein T represents one or more of Al, B, P, fe, ti, W, ge, sn.
3. The method of claim 1, wherein the aluminosilicate compound comprises any one or more of pyroxene, kaolin, talc, mica, montmorillonite, silica, feldspar.
4. The method according to claim 1, wherein the etching treatment comprises any one of an acid treatment and an alkali treatment.
5. The method according to claim 4, wherein,
the acid in the acid treatment is selected from any one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, hydrofluoric acid and perchloric acid.
6. The method according to claim 4, wherein the acid concentration in the acid solution used for the acid treatment is 0.01-10mol/L, the treatment temperature is-10-200 ℃ and the treatment time is 1min-4d.
7. The method according to claim 4, wherein the alkali used in the alkali treatment is selected from any one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, strontium hydroxide, ammonia water, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
8. The method according to claim 7, wherein the alkali concentration in the alkali solution used for the alkali treatment is 0.01mol/L to 10mol/L, the treatment temperature is-10 ℃ to 200 ℃ and the treatment time is 1min to 4d.
9. A porous inorganic material for a battery, characterized by being prepared by the preparation method according to any one of claims 1 to 8.
10. A battery comprising an electrolyte, a separator, an anode active material layer, and a cathode active material layer, wherein any one or more of the electrolyte, the separator, the anode active material layer, and the cathode active material layer contains the porous inorganic material for a battery according to claim 9.
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