CN113206289A - Interface-free anti-pulverization all-glass solid sodium ion battery and preparation method thereof - Google Patents
Interface-free anti-pulverization all-glass solid sodium ion battery and preparation method thereof Download PDFInfo
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- CN113206289A CN113206289A CN202110422974.9A CN202110422974A CN113206289A CN 113206289 A CN113206289 A CN 113206289A CN 202110422974 A CN202110422974 A CN 202110422974A CN 113206289 A CN113206289 A CN 113206289A
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- 239000011521 glass Substances 0.000 title claims abstract description 253
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 73
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000007787 solid Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010298 pulverizing process Methods 0.000 title claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000002001 electrolyte material Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000007731 hot pressing Methods 0.000 claims abstract description 11
- 239000007772 electrode material Substances 0.000 claims description 67
- 239000002243 precursor Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 39
- 238000010791 quenching Methods 0.000 claims description 23
- 230000000171 quenching effect Effects 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 229910021645 metal ion Inorganic materials 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010410 dusting Methods 0.000 claims 1
- 239000006060 molten glass Substances 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 238000009417 prefabrication Methods 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 description 8
- -1 iron ions Chemical class 0.000 description 6
- 238000000713 high-energy ball milling Methods 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 229910001456 vanadium ion Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910003641 H2SiO3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910017677 NH4H2 Inorganic materials 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an interface-free anti-pulverization all-glass solid sodium ion battery and a preparation method thereof. The glass electrode and the glass electrolyte material in the battery are subjected to preparation, crushing and refining, prefabrication and hot pressing to realize one-time sintering forming of the battery. During hot press forming, the glass electrode and the glass electrolyte soften and intimately bond with each other and remain in a glass state, so that the interface between the electrolyte and the electrode is eliminated. In addition, the internal structure which is looser compared with crystals or other glass systems can reduce the volume change of the material caused by the migration of sodium ions in the charging and discharging processes, so that the all-solid-state battery technology is not limited by the problem of material pulverization or cracking caused by the cyclic process. The processing method of the all-glass solid sodium ion battery is simple and feasible, and the prepared battery is compact in interior, high in mechanical property, low in cost and high in cost performance.
Description
Technical Field
The invention belongs to the field of batteries, relates to a preparation technology of an all-solid-state sodium ion battery, and particularly relates to an interface-free anti-pulverization all-glass solid-state sodium ion battery and a preparation method thereof.
Background
The sodium resource used by the sodium ion battery is sufficient in source and low in price, so that the sodium ion battery has more resource economic benefits compared with a commercial lithium ion battery; the all-solid-state battery has the characteristics of high safety, long service life and environmental friendliness, and does not have safety risks such as easy leakage, easy volatilization, flammability, explosion and the like. The all-solid-state sodium ion battery integrates the advantages of the two batteries, but the interfaces of the cathode and the anode of the all-solid-state battery and the electrolyte are solid/solid interfaces, so that the interface resistance is high, and the transmission efficiency of sodium ions is seriously influenced; in addition, when the all-solid-state battery is circulated, sodium ions are continuously extracted/inserted into the solid electrode material, so that the electrode material is easily pulverized and cracked, and the service life of the all-solid-state battery is shortened.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an all-glass solid sodium ion battery without interface and with anti-pulverization performance and a preparation method thereof, which not only eliminate solid/solid interfaces between a cathode and an anode and an electrolyte, but also enable the all-solid sodium ion battery to have the anti-pulverization and anti-cracking capability during circulation, and in addition, the battery can be formed at one time through hot pressing, and the processing technology is simple and easy to implement.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the utility model provides a no interface anti-pulverization's solid-state sodium ion battery of full glass, includes electrolyte and the electrode that adopts the glass material to make, its characterized in that: the electrolyte is made of a glass electrolyte material, the electrode is made of an electrode material formed by mixing the glass electrolyte material and a glass electrode material, and the glass electrolyte material comprises Na2O and a skeleton oxide, the glass electrode material including Na2O, a framework oxide and a valence-variable metal oxide as an oxygen redox, and the framework oxide in the glass electrolyte material and the glass electrode material are the same.
Preferably, the electrode material further comprises conductive particles to play a role in collecting current.
Preferably, the framework oxide is SiO2、P2O5、B2O3Any one or more of them, but not limited to these.
Preferably, the variable valence metal oxides are metal oxides of vanadium, iron and copper.
Preferably, Na in the glass electrolyte material is calculated by mass fraction2The content of O is 5-35%, and the rest is a framework oxide.
Preferably, the glass electrode material contains Na in a mass fraction2The content of O is 5-40%, the content of variable valence metal oxide is 10-50%, and the rest is framework oxide.
Preferably, the content of the framework oxide in the glass electrode material is 20-65% by mass fraction.
Preferably, the valence-variable metal oxide is V2O5、V2O3、Fe2O3、Fe3O4、CuO、Cu2Any one or more of O, but not limited to these.
The invention also provides a preparation method of the interface-free anti-pulverization all-glass solid sodium ion battery, which is characterized by comprising the following steps of:
(1) preparation of glass electrolyte material: weighing oxides or corresponding salts in the glass electrolyte material as precursors according to the component calculation, uniformly mixing, heating to 800-1300 ℃ to enable the glass electrolyte material to reach a molten state to obtain glass liquid, preserving heat for a period of time, taking out and quenching to obtain electrolyte glass;
(2) preparing a glass electrode material: according to the oxide or the corresponding salt in the glass electrode material as a precursor, preparing electrode glass according to the same method in the step (1) (namely weighing the oxide or the corresponding salt in the glass electrode material as a precursor according to the component calculation, uniformly mixing, heating to 800-1300 ℃, enabling the mixture to reach a molten state to obtain glass liquid, keeping the temperature for a period of time, taking out and quenching to obtain the electrode glass);
(3) crushing of glass materials: crushing and grinding the electrolyte glass prepared in the step (1) and the glass electrode obtained in the step (2) to obtain electrolyte glass powder and electrode glass powder;
(4) assembling and prefabricating an all-glass solid sodium ion battery: adding conductive particles and electrolyte glass powder into the electrode glass powder, uniformly mixing to obtain an electrode material, and alternately layering and filling the electrode material and the electrolyte glass powder in a mould according to the sequence of electrode-electrolyte-electrode; prepressing the layering in the die by using a tablet press to obtain a battery prefabricated piece;
(5) carrying out hot pressing or sintering molding on the battery prefabricated sheet in the step (4), softening and fusing glass materials, and eliminating an interface between an electrode and an electrolyte to obtain a solid-state sodium-ion battery precursor;
(6) and (4) polarizing the electrodes at two sides of the solid sodium ion battery precursor obtained in the step (5) to enable metal ions of valence metal oxides in the two electrodes to be in different valence states, taking the electrode of high valence metal ions as an anode and the electrode of low valence metal ions as a cathode, and polarizing to obtain the interface-free anti-pulverization all-glass solid sodium ion battery.
Preferably, in step (1), the Na is2The precursor of O comprises Na2O、Na2CO3、Na2CO3·10H2O and NaHCO3Any one or more of them, but not limited to these.
With B2O3As framework oxide, the corresponding precursor comprises B2O3、H3BO3、NH4HB4O7、NH4HB4O7·3H2Any one or more of O, but not limited to these.
With P2O5As a framework oxide, the corresponding precursor comprises P2O5、NH4H2PO4、(NH4)2HPO4、NH4PO3Any one or more of them, but not limited to these.
With SiO2As framework oxides, the corresponding precursors comprise SiO2、H2SiO3、Si(OCH3)4Any one or more of them, but not limited to these.
Preferably, in the step (1), the holding time of the glass liquid is 5-300 min.
Preferably, step (1), said quenching includes, but is not limited to, a metal plate quenching method, a water quenching method, a graphite mold quenching method, and a metal cylinder quenching method.
Preferably, in the step (3), the crushing and grinding methods include, but are not limited to, a high-energy ball milling method, a jaw crusher grinding method and a friction crushing grinding method, and the particle sizes of the electrolyte glass powder and the electrode glass powder are both 0.5-50 μm.
Preferably, in the step (4), the conductive particles are any one or more of carbon nanotubes, conductive graphite, conductive carbon black and ketjen black.
Preferably, in the step (4), the mass percentage of the conductive particles in the electrode material is 0.5-15%.
Preferably, in the step (4), the electrolyte glass powder is added to the electrode material in a mass percentage of 10-40%.
Preferably, in the step (4), the battery prefabrication pressure is 1-20 MPa.
Preferably, in the step (4), in the step (5), the process equipment adopted for hot pressing or sintering molding comprises a common hot press, a vacuum hot press or discharge plasma sintering equipment, the preparation temperature of the hot pressing or sintering molding is 200-500 ℃, and the preparation pressure is 20-200 MPa.
The specific process for polarization in step (6) is not limited, and the existing techniques may be used.
The invention realizes the one-time sintering and forming of the battery by preparing, crushing, refining, prefabricating and hot pressing the glass materials (including the glass electrolyte material and the glass electrode material). During hot press forming, the glass electrode and the glass electrolyte soften and intimately bond with each other and remain in a glass state, so that the interface between the electrolyte and the electrode is eliminated.
In summary, the invention has the following advantages:
(1) in the all-glass solid sodium ion battery, the electrodes and the electrolyte are made of glass materials with similar skeleton structures, and when the all-glass solid sodium ion battery is subjected to hot press forming, the glass electrodes and the glass electrolyte are softened and closely combined with each other and still keep a glass state, so that an interface between the electrolyte and the electrodes is eliminated, sodium ions can be efficiently transmitted inside the battery through the same type of glass skeleton, and the performance of the solid battery is greatly improved.
(2) During repeated charging and discharging processes, sodium ions continuously move back and forth between a cathode and an anode in the battery, so that the volume of an electrode material is continuously changed, and stress generated by the volume change is easy to cause pulverization or cracking of the electrode material. The glass material used in the invention provides a convenient channel for the transmission of sodium ions due to the unique open three-dimensional network structure, and meanwhile, compared with a crystal or other glass systems, the loose internal structure can reduce the volume change of the material caused by the migration of sodium ions in the charging and discharging processes, so that the all-solid-state battery technology is not limited by the problem of material pulverization or cracking caused by the cyclic process.
(3) The processing method of the all-glass solid sodium ion battery is simple and easy to implement, and under the condition of hot pressing, the electrode glass material with a similar skeleton structure and the electrolyte glass material are softened and fused, so that the battery is formed at one time, and the prepared battery has enough mechanical strength. The obtained all-glass battery is crushed, and fractures are observed under a scanning electron microscope, so that defects such as air holes do not exist.
(4) The all-glass solid sodium ion battery related by the invention has high cost performance, the used glass material is based on sodium, the source is rich, the price is low, and the rest oxides in the glass are common oxides. The ionic conductivity of the glass system can reach 2X 10 at room temperature-5S·cm-1The room temperature ionic conductivity and chemical stability of the glass material are far superior to those of the traditional glass material.
Drawings
Fig. 1 is a schematic diagram of the structure and preparation process of an all-glass solid-state sodium ion battery.
Fig. 2 is a schematic diagram of the working principle of the all-glass solid-state sodium ion battery of the invention.
FIG. 3 shows the X-ray diffraction patterns of all-glass solid-state sodium-ion batteries manufactured in examples 1-4 of the present invention after being crushed by grinding.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The invention provides a preparation method of an interface-free anti-pulverization all-glass solid sodium ion battery, which comprises the following steps:
(1) preparation of glass electrolyte material: weighing oxides or corresponding salts in the glass electrolyte material as precursors according to the component calculation, uniformly mixing, heating to 800-1300 ℃ to enable the glass electrolyte material to reach a molten state to obtain glass liquid, preserving heat for a period of time, taking out and quenching to obtain electrolyte glass;
(2) preparing a glass electrode material: according to the oxide or the corresponding salt in the glass electrode material as a precursor, preparing electrode glass according to the same method in the step (1) (namely weighing the oxide or the corresponding salt in the glass electrode material as a precursor according to the component calculation, uniformly mixing, heating to 800-1300 ℃, enabling the mixture to reach a molten state to obtain glass liquid, keeping the temperature for a period of time, taking out and quenching to obtain the electrode glass);
(3) crushing of glass materials: crushing and grinding the electrolyte glass prepared in the step (1) and the glass electrode obtained in the step (2) to obtain electrolyte glass powder and electrode glass powder;
(4) assembling and prefabricating an all-glass solid sodium ion battery: adding conductive particles and electrolyte glass powder into the electrode glass powder, uniformly mixing to obtain an electrode material, and alternately layering and filling the electrode material and the electrolyte glass powder in a mould according to the sequence of electrode-electrolyte-electrode; prepressing the layering in the die by using a tablet press to obtain a battery prefabricated piece;
(5) carrying out hot pressing or sintering molding on the battery prefabricated sheet in the step (4), softening and fusing glass materials, and eliminating an interface between an electrode and an electrolyte to obtain a solid-state sodium-ion battery precursor, as shown in figure 1;
(6) and (3) polarizing the electrodes at two sides of the solid sodium ion battery precursor obtained in the step (5) to enable metal ions of valence metal oxides in the two electrodes to be in different valence states, wherein the electrode of high valence metal ions is a positive electrode, the electrode of low valence metal ions is a negative electrode, and polarizing to obtain the interface-free anti-pulverization all-glass solid sodium ion battery, as shown in fig. 1.
The invention is a non-interface anti-powdering full glassThe operation principle of the glass solid state sodium ion battery is shown in fig. 2, taking vanadium as a valence-variable metal as an example, after electrode glass powder is obtained by grinding in the step (3), reducing gas (such as hydrogen gas) is introduced to lead +5 valence vanadium (V) in the electrode glass powder2O5) Reduction to + 4V, and in step (6) polarization of one of the two electrodes to high V by polarization+5Low Na content+The other is polarized to high V+3Low Na content+The negative electrode of (1). In the discharging process of the battery, the + 3-valent vanadium ions in the cathode of the battery are converted into + 4-valent vanadium ions, the process provides electrons for an external circuit, and the battery does work outwards; at the same time, the + 5V ions in the positive electrode of the battery are converted into electrons to + 4V ions, and in order to balance the charges, the sodium ions in the negative electrode move to the positive electrode through the solid electrolyte. The charging process of the battery is exactly the reverse of this process.
Example 1
Selection of glass electrode material and glass electrolyte material: the glass electrolyte material is selected from: 15Na2O-50P2O5-35B2O3(ii) a The glass electrode material is selected from: 18Na2O-24Fe2O3-40 P2O5-18 B2O3(the number before the oxide is the molar fraction content).
The preparation process comprises the following steps:
(1) preparing a glass electrode material and a glass electrolyte material; according to the components and proportion of the glass electrode material and the glass electrolyte material, Na is adopted2CO3、NH4H2PO4、H3BO3As a glass electrolyte material Na2O、P2O5And B2O3And weighing the corresponding precursors according to the component calculation, uniformly mixing, heating to 1100 ℃ to enable the precursors to reach a molten state to obtain glass liquid, keeping the temperature for 2h, taking out and quenching to obtain the electrolyte glass. By using Na2CO3、NH4H2PO4、H3BO3And Fe2O3As a glass electrode material Na2O、P2O5、B2O3And Fe2O3And weighing the corresponding precursors according to the component calculation, uniformly mixing, heating to 1100 ℃, enabling the precursors to reach a molten state to obtain glass liquid, keeping the temperature for 2 hours, taking out, and quenching to obtain the electrode glass.
(2) Crushing of glass materials: and (2) crushing and grinding the electrode glass and the electrolyte glass in the step (1) by adopting a high-energy ball milling method, wherein the granularity is as fine as 5 mu m, and thus obtaining electrolyte glass powder and electrode glass powder.
(3) Assembling and prefabricating an all-glass solid sodium ion battery: the method comprises the steps of mixing conductive particles (12 mass percent) and electrolyte glass powder (15 mass percent) into a glass electrode material uniformly to obtain an electrode material, alternately layering and filling the electrode material and the electrolyte glass powder in a mould of a tablet press according to the sequence of electrode-electrolyte-electrode according to the structure shown in figure 1, and performing pre-pressing molding by using the tablet press to obtain a battery prefabricated piece, wherein the pre-pressing pressure is 4 MPa.
(4) Sintering and forming of the all-glass solid sodium ion battery: and (4) carrying out hot press forming on the battery prefabricated sheet prepared in the step (3) in a vacuum hot press, softening and fusing glass materials, and eliminating an interface between an electrode and an electrolyte to obtain a solid-state sodium-ion battery precursor. The preparation temperature is 400 ℃, and the preparation pressure is 80 MPa.
(5) And (4) polarizing the electrodes at two sides of the precursor of the solid sodium ion battery obtained in the step (4), so that the metal ions of the valence metal oxide in the two electrodes are in different valence states, namely one electrode has more iron ions with the valence of 3, the other electrode has more iron ions with the valence of 2, the electrode of the high valence metal ions is a positive electrode, the electrode of the low valence metal ions is a negative electrode, and polarizing to obtain the interface-free anti-pulverization all-glass solid sodium ion battery.
Example 2
Selection of glass electrode material and glass electrolyte material: the glass electrolyte material is selected from: 10Na2O-55SiO2-35B2O3The glass electrode material is selected as follows: 12Na2O-25V2O5-35SiO2-28B2O3(number before oxide)The words are mole fraction content). The preparation process comprises the following steps:
(1) preparing a glass electrode material and a glass electrolyte material; according to the components and proportion of the glass electrode material and the glass electrolyte material, Na is adopted2CO3、SiO2、H3BO3As a glass electrolyte material Na2O、SiO2And B2O3And weighing the corresponding precursors according to the component calculation, uniformly mixing, heating to 1200 ℃ to enable the precursors to reach a molten state to obtain glass liquid, preserving heat for 1.5h, taking out, and quenching to obtain the electrolyte glass. By using Na2CO3、SiO2、H3BO3、NH4VO3As a glass electrode material Na2O、SiO2、B2O3And V2O5And weighing the corresponding precursors according to the component calculation, uniformly mixing, heating to 1200 ℃ to enable the precursors to reach a molten state to obtain glass liquid, preserving heat for 1.5h, taking out, and quenching to obtain the electrode glass.
(2) Crushing of glass materials: and (2) crushing and grinding the electrode glass and the electrolyte glass in the step (1) by adopting a high-energy ball milling method, wherein the granularity is as fine as 2 mu m, and thus obtaining electrolyte glass powder and electrode glass powder.
(3) Assembling and prefabricating an all-glass solid sodium ion battery: the method comprises the steps of mixing conductive particles (10 mass percent) and electrolyte glass powder (18 mass percent) into a glass electrode material uniformly to obtain an electrode material, alternately layering and filling the electrode material and the electrolyte glass powder in a mould of a tablet press according to the sequence of electrode-electrolyte-electrode according to the structure shown in figure 1, and performing pre-pressing molding by using the tablet press to obtain a battery prefabricated piece, wherein the pre-pressing pressure is 10 MPa.
(4) Sintering and forming of the all-glass solid sodium ion battery: and (4) carrying out hot press forming on the battery prefabricated sheet prepared in the step (3) in a vacuum hot press, softening and fusing glass materials, and eliminating an interface between an electrode and an electrolyte to obtain a solid-state sodium-ion battery precursor. The preparation temperature is 450 ℃, and the preparation pressure is 160 MPa.
(5) And (4) polarizing the electrodes at two sides of the precursor of the solid sodium ion battery obtained in the step (4), so that the metal ions of the valence metal oxide in the two electrodes are in different valence states, namely one electrode has more iron vanadium ions with valence of 5, the other electrode has more vanadium ions with valence of 3, the electrode of the high valence metal ions is a positive electrode, the electrode of the low valence metal ions is a negative electrode, and polarizing to obtain the interface-free anti-pulverization all-glass solid sodium ion battery.
Example 3
Selection of glass electrode material and glass electrolyte material: the glass electrolyte material is selected from: 25Na2O-45P2O5-30B2O3The glass electrode material is selected as follows: 18Na2O-27Fe3O4-32 P2O5-23 B2O3(the number before the oxide is the molar fraction content). The preparation process comprises the following steps:
(1) preparing a glass electrode material and a glass electrolyte material; according to the components and proportion of the glass electrode material and the glass electrolyte material, Na is adopted2CO3、NH4H2PO4And H3BO3As a glass electrolyte material Na2O、P2O5And B2O3And weighing the corresponding precursors according to the component calculation, uniformly mixing, heating to 1200 ℃ to enable the precursors to reach a molten state to obtain glass liquid, preserving heat for 3h, taking out, and quenching to obtain the electrolyte glass. By using Na2CO3、NH4H2PO4、H3BO3、Fe3O4As a glass electrode material Na2O、P2O5、B2O3And Fe3O4And weighing the corresponding precursors according to the component calculation, uniformly mixing, heating to 1200 ℃ to enable the precursors to reach a molten state to obtain glass liquid, keeping the temperature for 3h, taking out and quenching to obtain the electrode glass.
(2) Crushing of glass materials: and (2) crushing and grinding the electrode glass and the electrolyte glass in the step (1) by adopting a high-energy ball milling method, wherein the granularity is as fine as 5 mu m, and thus obtaining electrolyte glass powder and electrode glass powder.
(3) Assembling and prefabricating an all-glass solid sodium ion battery: the method comprises the steps of mixing conductive particles (8 mass percent) and electrolyte glass powder (24 mass percent) into a glass electrode material uniformly to obtain an electrode material, alternately layering and filling the electrode material and the electrolyte glass powder in a mould of a tablet press according to the sequence of electrode-electrolyte-electrode according to the structure shown in figure 1, and performing pre-pressing molding by using the tablet press to obtain a battery prefabricated piece, wherein the pre-pressing pressure is 16 MPa.
(4) Sintering and forming of the all-glass solid sodium ion battery: and (3) sintering and forming the cell prefabricated sheet prepared in the step (3) in a discharge plasma sintering furnace, softening and fusing glass materials, and eliminating an interface between an electrode and an electrolyte to obtain a solid sodium-ion cell precursor. The preparation temperature is 390 ℃, and the preparation pressure is 120 MPa.
(5) And (4) polarizing the electrodes at two sides of the precursor of the solid sodium ion battery obtained in the step (4), so that the metal ions of the valence metal oxide in the two electrodes are in different valence states, namely one electrode has more iron ions with the valence of 3, the other electrode has more iron ions with the valence of 2, the electrode of the high valence metal ions is a positive electrode, the electrode of the low valence metal ions is a negative electrode, and polarizing to obtain the interface-free anti-pulverization all-glass solid sodium ion battery.
Example 4
Selection of glass electrode material and glass electrolyte material: the glass electrolyte material is selected from: 30Na2O-42SiO2-28B2O3The glass electrode material is selected as follows: 19Na2O-27V2O3-32SiO2-22 B2O3(the number before the oxide is the molar fraction content). The preparation process comprises the following steps:
(1) preparing a glass electrode material and a glass electrolyte material; according to the components and proportion of the glass electrode material and the glass electrolyte material, Na is adopted2CO3、SiO2、H3BO3As a glass electrolyte material Na2O、SiO2And B2O3The corresponding precursors are weighed according to the component calculation and then mixed evenly,heating to 1050 ℃ to reach a molten state to obtain glass liquid, keeping the temperature for 2h, taking out and quenching to obtain the electrolyte glass. By using Na2CO3、SiO2、H3BO3、V2O3As a glass electrode material Na2O、SiO2、B2O3And V2O3And weighing the corresponding precursors according to the component calculation, uniformly mixing, heating to 1050 ℃ to enable the precursors to reach a molten state to obtain glass liquid, keeping the temperature for 2h, taking out and quenching to obtain the electrode glass.
(2) Crushing of glass materials: and (2) crushing and grinding the electrode glass and the electrolyte glass in the step (1) by adopting a high-energy ball milling method, wherein the granularity is as fine as 1 mu m, and thus obtaining electrolyte glass powder and electrode glass powder.
(3) Assembling and prefabricating an all-glass solid sodium ion battery: the method comprises the steps of mixing conductive particles (6 mass percent) and electrolyte glass powder (35 mass percent) into a glass electrode material uniformly to obtain an electrode material, alternately layering and filling the electrode material and the electrolyte glass powder in a mould of a tablet press according to the sequence of electrode-electrolyte-electrode according to the structure shown in figure 1, and performing pre-pressing molding by using the tablet press to obtain a battery prefabricated piece, wherein the pre-pressing pressure is 12 MPa.
(4) Sintering and forming of the all-glass solid sodium ion battery: and (3) sintering and forming the all-glass solid sodium ion battery prefabricated sheet prepared in the step (3) in a discharge plasma sintering furnace, softening and fusing glass materials, and eliminating an interface between an electrode and an electrolyte to obtain a solid sodium ion battery precursor. The preparation temperature is 375 ℃, and the preparation pressure is 160 MPa.
(5) And (4) polarizing the electrodes at two sides of the precursor of the solid sodium ion battery obtained in the step (4), so that the metal ions of the valence metal oxide in the two electrodes are in different valence states, namely one electrode has more iron ions with the valence of 3, the other electrode has more iron ions with the valence of 2, the electrode of the high valence metal ions is a positive electrode, the electrode of the low valence metal ions is a negative electrode, and polarizing to obtain the interface-free anti-pulverization all-glass solid sodium ion battery.
The all-glass solid-state sodium ion battery obtained in example 1 had sufficient mechanical strength (compressive strength of 130 MPa). The X-ray diffraction pattern of the all-glass solid sodium ion battery prepared in the embodiments 1 to 4 after grinding and crushing is shown in fig. 3 (corresponding to the curves "sample 01 to 04" in fig. 3 respectively), and no obvious characteristic peak can be seen, which indicates that the material in the battery still maintains the glass state.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention and are equivalent to the replacement of the above embodiments are included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a no interface anti-pulverization's solid-state sodium ion battery of full glass, includes electrolyte and the electrode that adopts the glass material to make, its characterized in that: the electrolyte is made of a glass electrolyte material, the electrode is made of an electrode material formed by mixing the glass electrolyte material and a glass electrode material, and the glass electrolyte material comprises Na2O and a skeleton oxide, the glass electrode material including Na2O, a framework oxide and a valence-variable metal oxide as an oxygen redox, and the framework oxide in the glass electrolyte material and the glass electrode material are the same.
2. The full glass solid state sodium ion battery of claim 1, wherein the full glass solid state sodium ion battery is characterized by: the skeleton oxide is SiO2、P2O5、B2O3The variable valence metal oxide is metal oxide of vanadium, iron and copper.
3. The full glass solid state sodium ion battery of claim 1, wherein the full glass solid state sodium ion battery is characterized by: na in the glass electrolyte material2The content of O is 5-35%; na in the glass electrode material2The content of O is 5-40%.
4. The full glass solid state sodium ion battery of claim 1, wherein the full glass solid state sodium ion battery is characterized by: the valence-variable metal oxide is V2O5、V2O3、Fe2O3、Fe3O4、CuO、Cu2And any one or more of O.
5. A method for preparing the interface-free anti-dusting all-glass solid-state sodium ion battery of any one of claims 1-4, comprising the steps of:
(1) preparation of glass electrolyte material: weighing oxides or corresponding salts in the glass electrolyte material as precursors according to the component calculation, uniformly mixing, heating to 800-1300 ℃ to enable the glass electrolyte material to reach a molten state to obtain glass liquid, preserving heat for a period of time, taking out and quenching to obtain electrolyte glass;
(2) preparing a glass electrode material: preparing electrode glass according to the same method in the step (1) by taking oxides or corresponding salts in the glass electrode material as precursors;
(3) crushing of glass materials: crushing and grinding the electrolyte glass prepared in the step (1) and the glass electrode obtained in the step (2) to obtain electrolyte glass powder and electrode glass powder;
(4) assembling and prefabricating an all-glass solid sodium ion battery: adding conductive particles and electrolyte glass powder into the electrode glass powder, uniformly mixing to obtain an electrode material, and alternately layering and filling the electrode material and the electrolyte glass powder in a mould according to the sequence of electrode-electrolyte-electrode; prepressing the layering in the die by using a tablet press to obtain a battery prefabricated piece;
(5) carrying out hot pressing or sintering molding on the battery prefabricated sheet in the step (4), softening and fusing glass materials, and eliminating an interface between an electrode and an electrolyte to obtain a solid-state sodium-ion battery precursor;
(6) and (4) polarizing the electrodes at two sides of the solid sodium ion battery precursor obtained in the step (5) to enable metal ions of valence metal oxides in the two electrodes to be in different valence states, taking the electrode of high valence metal ions as an anode and the electrode of low valence metal ions as a cathode, and polarizing to obtain the interface-free anti-pulverization all-glass solid sodium ion battery.
6. The method of claim 5, wherein: in the step (1), the Na is2The precursor of O comprises Na2O、Na2CO3、Na2CO3·10H2O and NaHCO3。
7. The method of claim 5, wherein: and (1) keeping the temperature of the molten glass for 5-300min, wherein quenching comprises a metal plate quenching method, a water quenching method, a graphite mold quenching method and a metal cylinder quenching method.
8. The method of claim 5, wherein: in the step (3), the crushing and grinding methods comprise a high-energy ball grinding method, a jaw crusher grinding method and a friction crushing grinding method, and the obtained electrolyte glass powder and the electrode glass powder have the particle sizes of 0.5-50 mu m.
9. The method of claim 5, wherein: in the step (4), the conductive particles are any one or more of carbon nanotubes, conductive graphite, conductive carbon black and Keqin black; the mass percentage of the conductive particles in the electrode material is 0.5-15%; the mass percentage of the electrolyte glass powder added into the electrode material is 10-40%; the battery prefabricating pressure is 1-20 MPa.
10. The method of claim 5, wherein: in the step (5), the process equipment adopted for hot pressing or sintering molding comprises a common hot press, a vacuum hot press or discharge plasma sintering equipment, the preparation temperature of the hot pressing or sintering molding is 200-500 ℃, and the preparation pressure is 20-200 MPa.
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