CN118047414A - Solid electrolyte precursor, solid electrolyte and preparation method thereof - Google Patents
Solid electrolyte precursor, solid electrolyte and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 109
- 239000002243 precursor Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 77
- 239000000243 solution Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 61
- 238000001035 drying Methods 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 38
- 239000007853 buffer solution Substances 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 25
- 239000013067 intermediate product Substances 0.000 claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 230000009257 reactivity Effects 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 36
- 238000000498 ball milling Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 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 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009766 low-temperature sintering Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003746 solid phase reaction Methods 0.000 claims description 6
- -1 zirconium alcohols Chemical class 0.000 claims description 6
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical group [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 150000003376 silicon Chemical class 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 13
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 9
- 230000002159 abnormal effect Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 239000000377 silicon dioxide Substances 0.000 description 21
- 239000002245 particle Substances 0.000 description 13
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 11
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 description 6
- 229910004675 Na1+xZr2SixP3-xO12 Inorganic materials 0.000 description 5
- 229910004678 Na1+xZr2SixP3−xO12 Inorganic materials 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000010671 solid-state reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002228 NASICON Substances 0.000 description 2
- NYAWADGYOWCCLK-UHFFFAOYSA-N [Na].[Zr] Chemical compound [Na].[Zr] NYAWADGYOWCCLK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical compound C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- AXFLWPUWMOTLEY-UHFFFAOYSA-N oxosilicon(2+) oxygen(2-) zirconium(4+) Chemical compound [Si+2]=O.[O-2].[Zr+4].[O-2].[O-2] AXFLWPUWMOTLEY-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the field of sodium ion solid-state batteries, in particular to a solid-state electrolyte precursor, a solid-state electrolyte and a preparation method thereof, comprising the following steps: step one, dissolving a silicon source in a first solvent to obtain a first solution; dissolving a zirconium source in a second solvent to obtain a second solution; step two, preparing buffer solution; step three, dropwise adding the second solution into the buffer solution, and keeping stirring in the dropwise adding process; after stirring for a first preset time, dropwise adding a first solution; sealing the seal after the first solution is dripped, and continuously stirring for a second preset time; step four, centrifuging and drying the mixed solution obtained in the step three for the second preset time to obtain an intermediate product; and fifthly, preheating the intermediate product, heating to 800-950 ℃, and preserving heat for 3-5 hours to obtain the nanoscale solid electrolyte precursor with active reactivity. The method can solve the problems of abnormal growth of crystal grains, low ionic conductivity and the like in the existing sintering process of the sodium ion solid electrolyte.
Description
Technical Field
The invention relates to the field of sodium ion solid-state batteries, in particular to a solid-state electrolyte precursor, a solid-state electrolyte and a preparation method thereof.
Background
Since the advent of commercial lithium ion batteries, lithium ion batteries have taken the dominant role in the consumer electronics market, along with the increasing maturity of battery technology. At present, the traditional liquid lithium ion battery is difficult to improve the safety and the energy density at the same time, and the development of the field of new energy automobiles is restricted to a certain extent. Due to the high chemical and electrochemical stability, high thermal stability and high mechanical strength of the solid electrolyte, the all-solid-state battery is expected to realize the matching use of a high-energy positive electrode and a high-energy negative electrode, and has both high energy density and high safety.
The lithium metal resources are rare in earth reserves, high in price, extremely uneven in distribution and the like, so that the development of various lithium battery products is restricted. In recent years, sodium batteries have become research hot spots on various large platforms due to the characteristics of abundant resources, low cost, chemical properties similar to those of lithium batteries, and the like. Most of the sodium battery studies reported to date are liquid electrolytes based on organic solvents, such as ethers and carbonates. The flammability and leakage of organic solvents present potential safety issues for liquid sodium batteries. In contrast, the solid sodium battery has the advantages of high stability, no leakage risk, easiness in direct stacking and processing and the like, and the safety performance of the battery is remarkably improved.
In solid state sodium batteries, sodium ion solid state electrolytes are the most critical component, with the NaSICON type Na 1+ xZr2SixP3−xO12 (0.ltoreq.x.ltoreq.3) solid state electrolyte system, initiated by Hong and Goodenough 40 years ago. NaSICON is a continuous solid solution formed by NaZr 2(PO4)3 and NaZr 2(SiO4)3, and has a general formula of Na 1+xZr2SixP3-xO12 (o.ltoreq.x.ltoreq.3), when x=2, that is, na 3Zr2Si2PO12 has the highest ionic conductivity, and can reach 0.2S/cm at a temperature of 300 ℃.
In this context, na 1+xZr2SixP3−xO12 (0.ltoreq.x.ltoreq.3) is synthesized mainly by the solid-state reaction process and the sol-gel process. Some specific cations, such as Al 3+、Yb3+、La3+、Nd3+、Y3+、Nb5+、Ti4+ and Zn 2+, were used as dopants to alter the sintering ability and crystal structure of NaSiCON by solid state reaction methods or to use sintering aids such as Na 2O-Nb2O5-P2O5 glass, antimony oxide, tin oxide, na 2O、Na2SiO3 and Na 3BO3 to enhance densification of Na 3Zr2Si2PO12.
Although the Nasicon type solid electrolyte has made a great breakthrough in performance, and the conductivity of Na ions is remarkably improved by a research method of cation substitution. But the rapid growth of grains during sintering severely hampers the search for bulk dense ceramic electrolytes with nanoscale structures. The conventional sintering process for solid ceramic electrolytes is to heat and sinter the raw materials at high temperatures (> 1200 ℃) until optimal densification is achieved. For this reason, the grain size of the NaSICON-type solid electrolyte sintered in the conventional manner increases significantly with densification, resulting in a micro-scale microstructure (grain size exceeding 1 mm). The solid electrolyte of micron-sized crystal grains has large grain boundary impedance, so that the overall ion conductivity of the electrolyte is low, and the electrolyte cannot be matched with high-voltage positive and negative electrodes.
NaSICON ceramic powders can also be synthesized by sol-gel processes, and the densification temperature of the NaSICON fines is typically higher than 1000 ℃ or lower than the precursor through the solid state reaction process, but the ceramic grain size remains micron-sized after the final stage sintering process. For example, mg-doped and Sc-doped NaSICON solid state electrolytes have a grain size in the range of 1mm to 2mm after sintering at a maximum temperature of 1260 ℃ according to literature "Lithium ion transport properties of high conductive tellurium substituted Li7La3Zr2O12cubic lithium garnets". According to the description of document INTERPHASEENGINEERING ENABLED ALL-ceramic lithium battery, na 3Zr2Si2PO12 shows a larger grain size in liquid phase sintering, about 4mm, in the presence of Na 3SiO3 additive.
In the research of NaSICON sodium ion solid electrolyte materials, the technology used in the result that the electrochemical performance is more than 4.5mS/cm is complex, and although the performance is good, the practical application requirement of the all-solid sodium battery can not be met.
CN116598579a discloses a preparation method of a locally ordered sodium zirconium phosphosilicate solid electrolyte and a battery, and the sodium source, the zirconium source, the silicon source, the phosphorus source and the doping element source are respectively ball-milled according to stoichiometric ratio and dried to obtain precursor powder a, precursor powder B, precursor powder C, precursor powder D, precursor powder E and precursor powder F; respectively calcining and grinding under sodium atmosphere to obtain corresponding initial samples; mixing more than two initial samples, ball milling, drying, pressing and sintering to obtain the locally ordered sodium zirconium phosphosilicate solid electrolyte. CN115472901a discloses a method for preparing NASICON type sodium ion solid electrolyte at low temperature. The method comprises the following steps: mixing anhydrous sodium carbonate, zirconia, silicon dioxide and ammonium dihydrogen phosphate, and then performing primary ball milling, primary drying and presintering to obtain precursor powder A; mixing the precursor powder A with CuO, and then performing secondary ball milling and secondary drying to obtain precursor powder B; and pressing the precursor powder B into a blank, then sintering, and cooling to obtain the NASICON type sodium ion solid electrolyte. The above solution is not a beneficial attempt in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a solid electrolyte precursor, a solid electrolyte and a preparation method thereof, which can solve the problems of abnormal growth of crystal grains, low ionic conductivity and the like in the existing sintering process of sodium ion solid electrolyte.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
In a first aspect, the present invention provides a method for preparing a solid electrolyte precursor, comprising the steps of:
Step one, dissolving a silicon source in a first solvent to obtain a first solution; dissolving a zirconium source in a second solvent to obtain a second solution;
Step two, preparing buffer solution;
step three, dropwise adding the second solution into the buffer solution, and keeping stirring in the dropwise adding process; after stirring for a first preset time, dropwise adding a first solution; sealing the seal after the first solution is dripped, and continuously stirring for a second preset time;
Step four, centrifuging and drying the mixed solution obtained in the step three for the second preset time to obtain an intermediate product;
And fifthly, preheating the intermediate product, and then heating and sintering to obtain the nanoscale solid electrolyte precursor with active reactivity.
By adopting the technical scheme, the first solution and the second solution are fully mixed in the buffer solution, and then the solid electrolyte precursor with active reactivity in nano level is obtained through centrifugation, drying, preheating and temperature rising sintering in sequence. The synthesis mechanism is as follows: monodisperse SiO 2 is synthesized on the basis of the formation of ZrO 2 particles in an alkaline environment, and since the SiO 2 particles are smaller than the ZrO 2 particles, the SiO 2 particles coat the surface of the ZrO 2 particles during the coprecipitation process. As sintering proceeds, the zirconium source gradually transforms into a metastable tetragonal phase zirconium dioxide ZrO 2, and the silicon dioxide SiO 2 formed by sintering the silicon source coats the zirconium dioxide surface. Because of the coating effect of the silicon dioxide, the zirconium dioxide can not be contacted with other substances in the cooling process of sintering, so that the zirconium dioxide can be kept in a metastable tetragonal crystal phase.
When the solid electrolyte precursor is adopted for preparing the solid electrolyte, the zirconium dioxide is kept in a tetragonal crystal phase in a metastable state, so that the growth of silicon dioxide in a monoclinic crystal phase is effectively inhibited, the phase forming temperature of the solid electrolyte is reduced, namely sintering treatment at a higher temperature is not needed, the nanocrystallization of the grain size of the solid electrolyte is realized, and the problem that the grain size is overlarge due to the conventional solid state reaction method is solved.
Further, in the first step, the silicon source is an ester substance of silicon, and the zirconium source is an alcohol substance of zirconium.
Further, in the first step, the silicon source is tetraethyl silicate or tetramethyl silicate, and the zirconium source is zirconium n-butoxide, zirconium n-propoxide or zirconium isopropoxide.
Further, ammonia water, deionized water and absolute ethyl alcohol are adopted to prepare a buffer solution in the second step, and the volume ratio of the ammonia water to the deionized water to the absolute ethyl alcohol is 1:1.2-1.5:2.8-3.3. The main purpose of ammonia water is to adjust the pH value of the buffer solution so as to keep the buffer solution in an alkaline state, and the mixed solution of deionized water and absolute ethyl alcohol is mainly used for better dispersing the oily solution and the aqueous solution.
Further, the third step is specifically: dropwise adding the second solution into the buffer solution, and keeping stirring in the dropwise adding process, wherein the stirring speed is set to 300-400 r/min; stirring for a first preset time, namely 5-10 min, and then dropwise adding a first solution;
After the first solution is added dropwise, sealing, continuously stirring for 5-10 min under the condition that the stirring speed is 300-400 r/min, adjusting the stirring speed to 150-250 r/min, and continuously stirring for a second preset time, namely 12-24 h.
Further, the fourth step is specifically: and (3) carrying out centrifugal treatment on the mixed solution obtained in the second preset time in the third step by adopting deionized water under the condition that the rotating speed is set to 7000-8000 r/min, centrifuging for 1-2 times by adopting absolute ethyl alcohol, and drying in a solid product blast oven obtained by centrifugation at the temperature of 60-80 ℃ for 3-5 hours to obtain an intermediate product.
Further, the preheating temperature in the fifth step is set to be 350-400 ℃, and the preheating time is set to be 3-5 hours; and fifthly, setting the temperature rise sintering temperature to be 800-950 ℃ and setting the heat preservation time to be 3-5 h.
In a second aspect, the present invention provides a solid electrolyte precursor prepared by the above method for preparing a solid electrolyte precursor.
In a third aspect, the present invention provides a method of preparing a solid electrolyte comprising the steps of:
1) Weighing a sodium source, a phosphorus source and a solid electrolyte precursor prepared by adopting the preparation method of the solid electrolyte precursor according to the chemical general formula of the solid electrolyte;
2) Preparing solid electrolyte material powder by a solid phase reaction method through adopting a sodium source, a phosphorus source and a solid electrolyte precursor which are weighed in the step 1);
3) Ball milling, drying, tabletting and sintering are carried out on the solid electrolyte material powder to obtain the solid electrolyte.
Further, the step 2) specifically comprises:
Firstly, ball milling and drying are carried out on the sodium source, the phosphorus source and the solid electrolyte precursor weighed in the step 1), wherein the ball milling conditions are as follows: ball milling for 10-15 h by a wet method, wherein a ball milling medium is absolute ethyl alcohol or isopropanol; the drying conditions are as follows: drying in a blast oven at the temperature of 60-80 ℃ for 3-5 hours;
And then sintering the mixture into solid electrolyte material powder at a low temperature, wherein the low-temperature sintering conditions are as follows: and (3) preserving heat for 9-12 hours in an air atmosphere at the temperature of 800-950 ℃, wherein the temperature rising speed is set to be 5-10 ℃/min.
Further, the ball milling conditions in step 3) are: ball milling for 10-15 h by a wet method, wherein a ball milling medium is absolute ethyl alcohol or isopropanol;
the drying conditions are as follows: drying in a blast oven at 60-80 ℃ for 3-5 hours;
the tabletting conditions are as follows: the pressure of the compression molding is 6-10 MPa;
the sintering conditions are as follows: and (3) preserving heat for 12-16 hours in an air atmosphere at the temperature of 1100-1260 ℃, setting the heating speed to 5-10 ℃/min, taking out the experimental sample after sintering, and polishing to obtain the massive compact solid electrolyte.
In a fourth aspect, the present invention provides a solid electrolyte prepared by the method for preparing a solid electrolyte as described above.
The invention has the beneficial effects that:
1. By adopting the preparation method of the solid electrolyte precursor, the tetragonal phase crystal structure of zirconium dioxide ZrO 2 of the obtained zirconium oxide-silicon oxide solid electrolyte precursor is ensured to be in a metastable state, and silicon dioxide SiO 2 is coated on the surface of the tetragonal phase crystal ZrO 2 in an amorphous state, so that the stable and main monoclinic ZrO 2 phase which is the same as that of the original monoclinic zirconia and impurities such as Na 3PO4、Na4SiO4 and the like generated in the conventional solid-phase method for preparing the NaSICON solid electrolyte are effectively avoided. And because the silicon dioxide is adopted for coating, the silicon dioxide can be used as a silicon element donor in the solid electrolyte, and compared with other inert coating layers, the novel impurity element is prevented from being introduced, and the preparation purity of the solid electrolyte is ensured.
2. According to the invention, silicon dioxide SiO 2 is coated on the surface of the zirconium dioxide with the tetragonal phase crystal structure in a metastable state through sintering treatment, so that the formation temperature of monoclinic solid electrolyte Na 1+xZr2SixP3−xO12 (0 < x < 3) is reduced, and meanwhile, the grain size is nanocrystallized, so that the grain boundary impedance of the solid electrolyte is small, the overall ion conductivity is higher, and the solid electrolyte can be matched with high-voltage positive and negative electrodes. And the subsequent densification of the same monoclinic Na 1+xZr2SixP3−xO12 (x is more than 0 and less than 3) is promoted, and the cycle performance of the ion conductivity battery of the electrolyte is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the description of the embodiments or the prior art will be briefly introduced below, it being obvious that the drawings in the description below are only some examples of the present invention.
Fig. 1 is a flowchart of a method for preparing a solid electrolyte precursor according to an embodiment of the present invention.
FIG. 2 is an X-ray diffraction pattern (model: XRD, bruker D2 PHASER, cu-K. Alpha.) of a zirconia-silica solid electrolyte precursor prepared in accordance with example one of the present invention.
FIG. 3 is a transmission electron microscope (TEM, JEM-2100F) of a zirconia-silica solid electrolyte precursor prepared according to the first embodiment of the present invention.
FIG. 4 is an X-ray diffraction pattern (model: XRD, bruker D2 PHASER, cu-K. Alpha.) of a NaSICON electrolyte powder prepared in example two of the present invention.
FIG. 5 is an SEM image (model: SEM 5000) of a NaSICON solid electrolyte prepared by low-temperature sintering by a method of pre-calcining zirconia-silica according to an embodiment of the present invention.
Fig. 6 shows the electrochemical impedance spectrum comparison of a NaSICON solid electrolyte sintered at low temperature by the method of precalcining zirconia-silica according to the embodiment of the present invention with a NaSICON solid electrolyte prepared by a conventional solid phase method (electrochemical workstation model: vantolab PGSTAT302N, switzerland).
FIG. 7 is an SEM image (model: SEM 5000) of a NaSICON solid electrolyte prepared by a conventional solid phase method in comparative example.
Detailed Description
Further advantages and effects of the present invention will become readily apparent to those skilled in the art from the disclosure herein, by referring to the accompanying drawings and the preferred embodiments. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be understood that the preferred embodiments are presented by way of illustration only and not by way of limitation.
It should be noted that the illustrations provided in the following embodiments merely illustrate the basic concept of the present invention by way of illustration, and only the components related to the present invention are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complicated.
In a first embodiment, a method for preparing a solid electrolyte precursor includes the steps of:
Step one, dissolving a silicon source in a first solvent to obtain a first solution; and dissolving a zirconium source in a second solvent to obtain a second solution. Specifically, 6.72mL of tetraethyl silicate (TEOS) is taken according to a general formula Na 3Zr2Si2PO12, and is dropwise added into 51.3mL of absolute ethyl alcohol at room temperature, and the mixture is uniformly stirred to obtain a first solution; 13.7mL of zirconium N-butoxide, i.e., zirconium source, was added to 13.7mL of N-methylpyrrolidone, i.e., NMP, and stirred well to give a second solution.
Step two, preparing buffer solution, specifically: 13mL of ammonia water is added into a mixed solution of 23mL of deionized water and 37mL of absolute ethyl alcohol, and the solution is stirred to a transparent solution by adopting a mechanical stirring mode, and the pH=7.5 of the buffer solution is ensured.
And thirdly, dropwise adding the second solution into the buffer solution, wherein stirring is kept in the dropwise adding process, and the stirring speed is 300r/min. After stirring for a first preset time, namely 5min, the first solution is dripped, and the stirring speed is 300r/min in the dripping process. After the first solution is dripped, sealing the bottle mouth by using a sealing film, continuously stirring for 5min under the condition of the stirring speed of 300r/min, then adjusting the stirring speed to 150r/min, and continuously stirring for a second preset time, namely 24h.
And step four, centrifuging and drying the mixed solution obtained in the step three and stirring for the second preset time to obtain an intermediate product. Specifically, the mixed solution obtained in the third step of stirring for the second preset time is subjected to centrifugal treatment for 3 times by adopting deionized water under the condition that the rotating speed is set to 7000-8000 r/min, and then is subjected to centrifugal treatment for 2 times by adopting absolute ethyl alcohol; and then drying the solid product obtained by centrifugation in a blast oven at 80 ℃ for 5 hours to obtain an intermediate product.
Step five, preheating the intermediate product in an air atmosphere, wherein the preheating temperature is set to 350 ℃, and the preheating time is set to 3 hours; then heating to 900 ℃, and preserving heat for 3 hours to obtain the nano-scale superfine binary particle solid electrolyte precursor with active reactivity.
Fig. 2 shows the XRD pattern of the prepared zirconia-silica solid electrolyte precursor, all diffraction peaks being attributable to tetragonal ZrO 2 structure, and there is no evidence of the formation of crystalline SiO 2 or zirconium salt crystals (ZrSiO 4). Tetragonal ZrO 2 is stabilized by the presence of the surface-coated SiO 2 matrix. The average size of tetragonal ZrO 2 particles was calculated to be 5.15. 5.15 nm from the diffraction of ZrO 2 at grain boundaries (111) according to the Scherrer formula.
Fig. 3 shows a TEM image of the prepared zirconia-silica solid electrolyte precursor, further confirming that the prepared zirconia-silica solid electrolyte precursor consists of uniform particles of less than 10 nm (about 5-10 nm).
In a second embodiment, a method for preparing a solid electrolyte includes the steps of:
1) The zirconia-silica solid electrolyte precursor prepared in the first embodiment is weighed by a balance, the error is reserved to the third position of the decimal point, the third position is converted into powder molar mass, and NaNO 3 and NH 4H2PO4 with corresponding stoichiometric amounts are weighed according to a chemical formula of Na 3Zr2Si2PO12.
2) Preparing solid electrolyte material powder, specifically: firstly ball milling and drying the raw materials weighed in the step 1), wherein the ball milling condition is wet ball milling for 10 hours, and the ball milling medium is isopropanol; the drying conditions are as follows: drying in a blast oven at 80 ℃ for 5 hours;
And then sintering the mixture into solid electrolyte material powder at a low temperature, wherein the low-temperature sintering conditions are as follows: the temperature is kept for 9 hours under the air atmosphere and the temperature is 900 ℃, and the temperature rising speed is set to be 5 ℃/min.
Fig. 4 is an XRD image of the prepared NaSICON electrolyte powder, confirming that the NaSICON solid electrolyte powder sintered at low temperature by the method of pre-calcining zirconia-silica is consistent with the conventional high temperature sintered NaSICON solid electrolyte.
3) Ball milling, drying, tabletting and sintering are carried out on the solid electrolyte material powder, wherein the ball milling conditions are as follows: ball milling for 10h by a wet method, wherein the ball milling medium is isopropanol; the drying conditions are as follows: drying in a blast oven at 80 ℃ for 5 hours; the tabletting conditions are as follows: the present invention is not particularly limited in the process and parameters of press molding, and a conventional press molding process and parameters may be employed, and preferably, the press molding pressure is set to 10MPa. The sintering conditions are as follows: and (3) preserving heat for 16 hours under the air atmosphere at the temperature of 1260 ℃, setting the heating speed to 5 ℃/min, taking out the experimental sample after sintering, and polishing to obtain the massive compact solid electrolyte Na 3Zr2Si2PO12.
Fig. 5 is an SEM image of a NaSICON solid electrolyte prepared by low temperature sintering by the method of pre-calcining zirconia-silica, which demonstrates that the grain size of the NaSICON solid electrolyte prepared by low temperature sintering by the method of pre-calcining zirconia-silica reaches the nano-scale, and the average grain size is 548±48nm.
Comparative example: a preparation method of a NaSICON type solid electrolyte comprises the following steps:
Firstly, weighing NaNO 3 powder, naNO or micron ZrO 2 powder, naNO or micron SiO 2 powder and NH 4H2PO4 powder according to the chemical formula Na 3Zr2Si2PO12 A kind of electronic device of the NaSICON solid electrolyte in a preset stoichiometric amount, adding the weighed NaNO 3 powder, zrO 2 powder, siO 2 powder and NH 4H2PO4 powder into a ball milling tank, adding a certain amount of isopropanol, and mixing and ball milling for 24 hours under the condition of 400r/min rotation speed to obtain slurry.
And step two, drying the slurry until the isopropanol is completely volatilized, wherein the drying temperature is 80 ℃. Then sintering treatment is carried out, the sintering temperature is 900 ℃, and the sintering time is 6 hours.
And thirdly, taking out the powder after furnace cooling, putting the powder into a ball milling tank, adding a certain amount of isopropanol, mixing and ball milling for 10 hours under the condition of 400r/min of rotating speed, and drying to obtain the NaSICON type electrolyte powder.
And step four, tabletting and sintering the powder obtained in the step sana to prepare the high-performance sodium ion solid electrolyte. Wherein, the tabletting conditions are as follows: the present invention is not particularly limited in the process and parameters of press molding, and a conventional press molding process and parameters may be employed, and preferably, the press molding pressure is 10MPa. The sintering conditions are as follows: and (3) preserving heat at 1260 ℃ for 16 hours in an air atmosphere, wherein the heating rate is 5 ℃/min, taking out the experimental sample after sintering, and polishing to obtain the NaSICON solid electrolyte, namely Na 3Zr2Si2PO12.
The SEM image of fig. 7 demonstrates that the NaSICON electrolyte sintered by the solid phase method has a larger particle size, and the crystal fracture mode is along the crystal fracture, and the electrolyte quality deviates.
Fig. 6 is a comparison of the electrochemical impedance spectra of a NaSICON solid electrolyte sintered at low temperature by the method of pre-calcining zirconia-silica according to the example of the present invention and a NaSICON solid electrolyte prepared by the comparative example, i.e., the conventional solid phase method, which demonstrates that the impedance of a NaSICON solid electrolyte sintered at low temperature by the method of pre-calcining zirconia-silica is much smaller than that of an electrolyte sintered by the conventional high temperature solid phase method in the comparative example.
In a third embodiment, a method for preparing a solid electrolyte precursor includes the steps of:
Step one, dissolving a silicon source in a first solvent to obtain a first solution; and dissolving a zirconium source in a second solvent to obtain a second solution. Specifically, tetramethyl silicate, i.e. a silicon source, is taken according to a general formula Na 3Zr2Si2PO12, and is added into absolute ethyl alcohol dropwise at room temperature, and the mixture is stirred uniformly to obtain a first solution. And adding zirconium drops of N-propanol, namely zirconium sources, into the N-methylpyrrolidone, and uniformly stirring to obtain a second solution.
Step two, preparing buffer solution, specifically: ammonia water is added into the mixed solution of deionized water and absolute ethyl alcohol, and the solution is stirred into a transparent solution by adopting a mechanical stirring mode, and the PH=7.5 of the buffer solution is ensured.
And thirdly, dropwise adding the second solution into the buffer solution, wherein stirring is kept in the dropwise adding process, and the stirring speed is 300r/min. After stirring for a first preset time, namely 5min, the first solution is dripped, and the stirring speed is 300r/min in the dripping process. After the first solution is dripped, sealing the bottle mouth by using a sealing film, continuously stirring for 5min under the condition of the stirring speed of 300r/min, then adjusting the stirring speed to 150r/min, and continuously stirring for a second preset time, namely 24h.
And step four, centrifuging and drying the mixed solution obtained in the step three and stirring for the second preset time to obtain an intermediate product. Specifically, the mixed solution obtained in the third step of stirring for the second preset time is subjected to centrifugal treatment for 3 times by adopting deionized water under the condition that the rotating speed is set to 7000-8000 r/min, and then is subjected to centrifugal treatment for 2 times by adopting absolute ethyl alcohol; and then drying the solid product obtained by centrifugation in a blast oven at 80 ℃ for 5 hours to obtain an intermediate product.
Step five, preheating the intermediate product in an air atmosphere, wherein the preheating temperature is set to 400 ℃, and the preheating time is set to 4 hours; then heating to 800 ℃, and preserving heat for 5 hours to obtain the nano-scale superfine binary particle solid electrolyte precursor with active reactivity.
In a fourth embodiment, a method for preparing a solid electrolyte precursor includes the steps of:
step one, dissolving a silicon source in a first solvent to obtain a first solution; and dissolving a zirconium source in a second solvent to obtain a second solution. Specifically, tetraethyl silicate, i.e., a silicon source, is taken according to the general formula Na 3Zr2Si2PO12, and is added into absolute ethyl alcohol dropwise at room temperature, and the mixture is stirred uniformly to obtain a first solution. And adding zirconium isopropoxide, namely a zirconium source, into the N-methylpyrrolidone, and uniformly stirring to obtain a second solution.
Step two, preparing buffer solution, specifically: ammonia water is added into the mixed solution of deionized water and absolute ethyl alcohol, and the solution is stirred into a transparent solution by adopting a mechanical stirring mode, and the PH=7.5 of the buffer solution is ensured.
And thirdly, dropwise adding the second solution into the buffer solution, wherein stirring is kept in the dropwise adding process, and the stirring speed is 350r/min. After stirring for a first preset time, namely 8min, the first solution is dripped, and the stirring speed is 350r/min in the dripping process. After the first solution is dripped, sealing the bottle mouth by using a sealing film, continuously stirring for 6min under the condition of the stirring speed of 250r/min, then adjusting the stirring speed to 150r/min, and continuously stirring for a second preset time, namely 12h.
And step four, centrifuging and drying the mixed solution obtained in the step three and stirring for the second preset time to obtain an intermediate product. Specifically, the mixed solution obtained in the third step of stirring for the second preset time is subjected to centrifugal treatment for 3 times by adopting deionized water under the condition that the rotating speed is set to 7000-8000 r/min, and then is subjected to centrifugal treatment for 2 times by adopting absolute ethyl alcohol; and then drying the solid product obtained by centrifugation in a blast oven at 80 ℃ for 5 hours to obtain an intermediate product.
Step five, preheating the intermediate product in an air atmosphere, wherein the preheating temperature is set to 350 ℃, and the preheating time is set to 5 hours; then heating to 950 ℃, and preserving heat for 3 hours to obtain the nano-scale superfine binary particle solid electrolyte precursor with active reactivity.
In a fifth embodiment, a method for preparing a solid electrolyte precursor includes the steps of:
step one, dissolving a silicon source in a first solvent to obtain a first solution; and dissolving a zirconium source in a second solvent to obtain a second solution. Specifically, tetraethyl silicate, i.e., a silicon source, is taken according to the general formula Na 3Zr2Si2PO12, and is added into absolute ethyl alcohol dropwise at room temperature, and the mixture is stirred uniformly to obtain a first solution. And adding zirconium isopropoxide, namely a zirconium source, into the N-methylpyrrolidone, and uniformly stirring to obtain a second solution.
Step two, preparing buffer solution, specifically: ammonia water is added into the mixed solution of deionized water and absolute ethyl alcohol, and the solution is stirred into a transparent solution by adopting a mechanical stirring mode, and the PH=7.5 of the buffer solution is ensured.
And thirdly, dropwise adding the second solution into the buffer solution, wherein stirring is kept in the dropwise adding process, and the stirring speed is 400r/min. After stirring for a first preset time, namely 10min, the first solution is added dropwise, and the stirring speed is 400r/min in the same way. After the first solution is dripped, sealing the bottle mouth by using a sealing film, continuously stirring for 10min under the condition of stirring speed of 150r/min, then adjusting the stirring speed to 150r/min, and continuously stirring for a second preset time, namely 16h.
And step four, centrifuging and drying the mixed solution obtained in the step three and stirring for the second preset time to obtain an intermediate product. Specifically, the mixed solution obtained in the third step of stirring for the second preset time is subjected to centrifugal treatment for 3 times by adopting deionized water under the condition that the rotating speed is set to 7000-8000 r/min, and then is subjected to centrifugal treatment for 2 times by adopting absolute ethyl alcohol; and then drying the solid product obtained by centrifugation in a blast oven at 80 ℃ for 5 hours to obtain an intermediate product.
Step five, preheating the intermediate product in an air atmosphere, wherein the preheating temperature is set to 400 ℃ and the preheating time is set to 5 hours; then heating to 920 ℃, and preserving heat for 4.5 hours to obtain the nano-scale superfine binary particle solid electrolyte precursor with active reactivity.
In a sixth embodiment, a method for preparing a solid electrolyte precursor includes the steps of:
Step one, dissolving a silicon source in a first solvent to obtain a first solution; and dissolving a zirconium source in a second solvent to obtain a second solution. Specifically, tetramethyl silicate, i.e. a silicon source, is taken according to a general formula Na 3Zr2Si2PO12, and is added into absolute ethyl alcohol dropwise at room temperature, and the mixture is stirred uniformly to obtain a first solution. And adding zirconium N-butoxide drops, namely zirconium sources, into the N-methylpyrrolidone, and uniformly stirring to obtain a second solution.
Step two, preparing buffer solution, specifically: ammonia water is added into the mixed solution of deionized water and absolute ethyl alcohol, and the solution is stirred into a transparent solution by adopting a mechanical stirring mode, and the PH=7.5 of the buffer solution is ensured.
And thirdly, dropwise adding the second solution into the buffer solution, wherein stirring is kept in the dropwise adding process, and the stirring speed is 350r/min. After stirring for a first preset time, namely 6min, the first solution is dripped, and the stirring speed is 350r/min in the dripping process. After the first solution is dripped, sealing the bottle mouth by using a sealing film, continuously stirring for 10min under the condition of the stirring speed of 350r/min, then adjusting the stirring speed to 200r/min, and continuously stirring for a second preset time, namely 18h.
And step four, centrifuging and drying the mixed solution obtained in the step three and stirring for the second preset time to obtain an intermediate product. Specifically, the mixed solution obtained in the third step of stirring for the second preset time is subjected to centrifugal treatment for 3 times by adopting deionized water under the condition that the rotating speed is set to 7000-8000 r/min, and then is subjected to centrifugal treatment for 2 times by adopting absolute ethyl alcohol; and then drying the solid product obtained by centrifugation in a blast oven at 80 ℃ for 5 hours to obtain an intermediate product.
Step five, preheating the intermediate product in an air atmosphere, wherein the preheating temperature is set to be 380 ℃, and the preheating time is set to be 4.5 hours; then heating to 900 ℃, and preserving heat for 3 hours to obtain the nano-scale superfine binary particle solid electrolyte precursor with active reactivity.
The above embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention.
Claims (12)
1. A method for preparing a solid electrolyte precursor, comprising the steps of:
Step one, dissolving a silicon source in a first solvent to obtain a first solution; dissolving a zirconium source in a second solvent to obtain a second solution;
Step two, preparing buffer solution;
step three, dropwise adding the second solution into the buffer solution, and keeping stirring in the dropwise adding process; after stirring for a first preset time, dropwise adding a first solution; sealing the seal after the first solution is dripped, and continuously stirring for a second preset time;
Step four, centrifuging and drying the mixed solution obtained in the step three for the second preset time to obtain an intermediate product;
and fifthly, preheating the intermediate product, and then heating and sintering to obtain the nanoscale solid electrolyte precursor with active reactivity.
2. The method for producing a solid electrolyte precursor according to claim 1, characterized in that: the silicon source in the first step is silicon esters, and the zirconium source is zirconium alcohols.
3. The method for producing a solid electrolyte precursor according to claim 2, characterized in that: the silicon source in the first step is tetraethyl silicate or tetramethyl silicate, and the zirconium source is zirconium n-butoxide, zirconium n-propoxide or zirconium isopropoxide.
4. The method for producing a solid electrolyte precursor according to claim 1 or 2, characterized in that: and in the second step, ammonia water, deionized water and absolute ethyl alcohol are adopted to prepare a buffer solution, wherein the volume ratio of the ammonia water to the deionized water to the absolute ethyl alcohol is 1:1.2-1.5:2.8-3.3.
5. The method for preparing a solid electrolyte precursor according to claim 1 or 2, wherein the step three is specifically: dropwise adding the second solution into the buffer solution, and keeping stirring in the dropwise adding process, wherein the stirring speed is set to 300-400 r/min; stirring for a first preset time, namely 5-10 min, and then dropwise adding a first solution;
After the first solution is added dropwise, sealing, continuously stirring for 5-10 min under the condition that the stirring speed is 300-400 r/min, adjusting the stirring speed to 150-250 r/min, and continuously stirring for a second preset time, namely 12-24 h.
6. The method for preparing a solid electrolyte precursor according to claim 1 or 2, wherein the step four is specifically: and (3) carrying out centrifugal treatment on the mixed solution obtained in the second preset time in the third step by adopting deionized water under the condition that the rotating speed is set to 7000-8000 r/min, centrifuging for 1-2 times by adopting absolute ethyl alcohol, and drying in a solid product blast oven obtained by centrifugation at the temperature of 60-80 ℃ for 3-5 hours to obtain an intermediate product.
7. The method for producing a solid electrolyte precursor according to claim 1 or 2, characterized in that: setting the preheating temperature in the fifth step to be 350-400 ℃ and the preheating time to be 3-5 h;
and fifthly, setting the temperature rise sintering temperature to be 800-950 ℃ and setting the heat preservation time to be 3-5 h.
8. A solid electrolyte precursor characterized by: the method for preparing a solid electrolyte precursor according to any one of claims 1 to 7.
9. A method for preparing a solid electrolyte, comprising the steps of:
1) Weighing a sodium source, a phosphorus source and a solid electrolyte precursor prepared by the preparation method of the solid electrolyte precursor according to any one of claims 1-7 according to a chemical general formula of the solid electrolyte;
2) Preparing solid electrolyte material powder by a solid phase reaction method through adopting a sodium source, a phosphorus source and a solid electrolyte precursor which are weighed in the step 1);
3) Ball milling, drying, tabletting and sintering are carried out on the solid electrolyte material powder to obtain the solid electrolyte.
10. The method for producing a solid electrolyte according to claim 9, wherein step 2) specifically comprises:
Firstly, ball milling and drying are carried out on the sodium source, the phosphorus source and the solid electrolyte precursor weighed in the step 1), wherein the ball milling conditions are as follows: ball milling for 10-15 h by a wet method, wherein a ball milling medium is absolute ethyl alcohol or isopropanol; the drying conditions are as follows: drying in a blast oven at the temperature of 60-80 ℃ for 3-5 hours;
And then sintering the mixture into solid electrolyte material powder at a low temperature, wherein the low-temperature sintering conditions are as follows: and (3) preserving heat for 9-12 hours in an air atmosphere at the temperature of 800-950 ℃, wherein the temperature rising speed is set to be 5-10 ℃/min.
11. The method for producing a solid electrolyte according to claim 9 or 10, wherein the ball milling conditions in step 3) are: ball milling for 10-15 h by a wet method, wherein a ball milling medium is absolute ethyl alcohol or isopropanol;
the drying conditions are as follows: drying in a blast oven at 60-80 ℃ for 3-5 hours;
the tabletting conditions are as follows: the pressure of the compression molding is 6-10 MPa;
the sintering conditions are as follows: and (3) preserving heat for 12-16 hours in an air atmosphere at the temperature of 1100-1260 ℃, setting the heating speed to 5-10 ℃/min, taking out the experimental sample after sintering, and polishing to obtain the massive compact solid electrolyte.
12. A solid state electrolyte characterized by: the method for producing a solid electrolyte according to any one of claims 9 to 11.
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