CN117623760A - NASICON type solid electrolyte, preparation method thereof and secondary battery - Google Patents
NASICON type solid electrolyte, preparation method thereof and secondary battery Download PDFInfo
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- CN117623760A CN117623760A CN202311627245.2A CN202311627245A CN117623760A CN 117623760 A CN117623760 A CN 117623760A CN 202311627245 A CN202311627245 A CN 202311627245A CN 117623760 A CN117623760 A CN 117623760A
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- solid electrolyte
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 62
- 239000002228 NASICON Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000007906 compression Methods 0.000 claims description 11
- 230000006835 compression Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 7
- 239000003570 air Substances 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 claims description 2
- 229910009496 Li1.5Al0.5Ge1.5 Inorganic materials 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009475 tablet pressing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
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Abstract
The invention provides a NASICON type solid electrolyte, a preparation method thereof and a secondary battery. The method comprises the following steps: carrying out dry ball milling on raw materials corresponding to the NASICON solid electrolyte, crushing once after finishing, tabletting once, and carrying out primary sintering on the material subjected to tabletting once to obtain a precursor material; and (3) secondarily crushing the precursor material, secondarily tabletting, and secondarily sintering the secondarily tableted material to obtain the NASICON type solid electrolyte. The invention optimizes the preparation method to ensure that the structure of the NASICON solid electrolyte is more compact, reduces the generation of air holes and improves the ionic conductivity.
Description
Technical Field
The invention belongs to the technical field of solid electrolyte materials, and particularly relates to a NASICON type solid electrolyte, a preparation method thereof and a secondary battery.
Background
The NASICON type solid electrolyte not only has the advantages of high thermal stability, good ion conductivity, wide potential window and the like, but also has certain stability in the aspect of chemical properties. In addition, the calcining density of the NASICON type solid electrolyte is relatively high, the environment is not polluted, and the process condition is controllable, so that the NASICON type solid electrolyte gradually becomes one of important materials of the all-solid power battery.
At present, the preparation method of the NASICON type solid electrolyte disclosed in the prior art mainly adopts a solid phase method to carry out one-time sintering to prepare the NASICON type solid electrolyte, or other substances are added to prepare the NASICON type solid electrolyte, so that the ion conductivity of the electrolyte is improved. However, the above method has disadvantages of low conductivity or complicated material preparation, and this also results in that the desired object is not achieved in terms of battery use.
In view of the above, there is a need to provide a preparation process that is easy to handle, thereby enabling to obtain a NASICON-type solid electrolyte having high ion conductivity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a NASICON type solid electrolyte, a preparation method thereof and a secondary battery. The invention optimizes the preparation method to ensure that the structure of the NASICON solid electrolyte is more compact, reduces the generation of air holes and improves the ionic conductivity.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of preparing a NASICON-type solid electrolyte, the method comprising the steps of:
carrying out dry ball milling on raw materials corresponding to the NASICON solid electrolyte, crushing once after finishing, tabletting once, and carrying out primary sintering on the material subjected to tabletting once to obtain a precursor material;
and (3) secondarily crushing the precursor material, secondarily tabletting, and secondarily sintering the secondarily tableted material to obtain the NASICON type solid electrolyte.
Aiming at the problems existing in the preparation of the NASICON type solid electrolyte sheet in the prior art, the invention adopts a method of continuously applying pressure in the step heating process to heat and fire, and the NASICON type solid electrolyte with short grain boundary distance and moderate grain size can be obtained because the synthesis effect (such as ionic conductivity) of the NASICON type solid electrolyte mainly consists of the grain growth size and the distance between grain boundaries, and the grain growth is a slow growth process in the heating process and in the heat preservation environment. In addition, in the synthesis process, due to the influence of impurities or moisture in raw materials, gas volatilizes in the solid electrolyte sheet during sintering, so that air holes in the electrolyte sheet are generated.
Preferably, the NASICON-type solid electrolyte comprises a LAGP solid electrolyte and/or a LATP solid electrolyte.
Preferably, the structural formula of the LAGP solid electrolyte is Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 。
Preferably, the structural formula of the LATP solid electrolyte is Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 。
Preferably, the feedstock comprises metal oxides and non-metal oxides.
Preferably, the metal oxide comprises any one or a combination of at least two of lithium oxide, aluminum oxide, germanium oxide or titanium oxide.
Preferably, the nonmetallic oxide includes any one of phosphorus pentoxide, phosphorus trioxide or a combination of at least two thereof.
Preferably, the dry ball milling speed is 200r/min-500r/min, preferably 300-480r/min, for example, 200r/min, 220r/min, 250r/min, 280r/min, 300r/min, 320r/min, 350r/min, 380r/min, 400r/min, 420r/min, 450r/min, 480r/min, 500r/min, etc.
In the invention, the raw materials are mixed more uniformly by regulating and controlling the speed of dry ball milling, the subsequent sintering process is facilitated, the raw materials are mixed unevenly due to the too low speed, the impurity of reaction products is increased, and otherwise, the raw materials are pre-reacted due to the too high ball milling energy.
Preferably, the dry ball milling time is 30min-1800min, preferably 120min-1500min, for example, 30min, 50min, 70min, 90min, 100min, 120r/min, 150r/min, 200r/min, 400r/min, 800r/min, 1000r/min, 1100r/min, 1200r/min, 1300r/min, 1400r/min, 1500r/min, 1600r/min, 1700r/min, 1800r/min, etc.
In the invention, the time of dry ball milling is required to be regulated according to the amount of materials, so that the granularity of raw material milling is finer, the mixing is more uniform, the too short time can lead to insufficient fineness of particles and uneven mixing, and otherwise, the material particles after ball milling can be flattened.
Preferably, the dry ball milling method is a positive and negative rotation alternating method, specifically, the conversion is performed every 0.5h, the process is stopped for 5-15min, preferably 5-10min, for example, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, etc.
In the invention, the forward and reverse transfer mode is used, so that the material is unnecessarily high in temperature during ball milling, a certain heat dissipation time can be provided in the process, and other side reaction processes caused by the high temperature are avoided. Preferably, the primary pulverization is carried out by using a vibration mill.
Preferably, the oscillation time of the vibration mill is 10s-5min, preferably 20s-1min, for example, 10s, 15s, 20s, 25s, 30s, 40s, 50s, 1min, 2min, 3min, 4min, 5min, etc.
Preferably, the pressure of the primary compression is 9-60Mpa, preferably 15-30 Mpa, for example, 9Mpa, 12Mpa, 15Mpa, 18Mpa, 20Mpa, 22Mpa, 25Mpa, 28Mpa, 30Mpa, 40Mpa, 50Mpa, 60Mpa, etc.
In the invention, the pressure of one-time tabletting is regulated, so that the material particles are well contacted, the particle contact is poor due to the too low pressure, so that insufficient reaction is caused, otherwise, the material is too compact, the requirement on a tabletting die is too high, and the pressed electrolyte sheet is too thin and fragile.
Preferably, the time of one compression is 15s-300s, preferably 60s-120s, for example, 15s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 180s, 200s, 300s, etc.
In the invention, the material particles are well contacted by regulating and controlling the time of one-time tabletting, the particles become loose again due to the rebound of force when the time is too short, and otherwise, the step time is wasted.
Preferably, the atmosphere of the primary sintering is any one of air, argon or nitrogen.
In the invention, the primary sintering can be performed in a muffle furnace, the upper end and the lower end of the muffle furnace are provided with special tungsten carbide pressure rods, and the pressure can be kept or increased in the sintering process by connecting a tablet press outside. The special tungsten carbide mold can also be made of other materials, such as silicon carbide, boron nitride or silicon nitride, and the like, preferably tungsten carbide.
Preferably, the primary sintering comprises the following processes: heating to 300-500deg.C, preferably 300-400deg.C, such as 300deg.C, 2500deg.C, 380deg.C, 400deg.C, 450deg.C, 480deg.C, 500deg.C, etc. at a rate of 3-5deg.C/min (such as 3deg.C/min, 3.5deg.C/min, 4deg.C/min, 5deg.C/min, etc.); the pressure is 0-60MPa, preferably 15-30 MPa, such as 2Mpa, 9Mpa, 12Mpa, 15Mpa, 18Mpa, 20Mpa, 22Mpa, 25Mpa, 28Mpa, 30Mpa, 40Mpa, 50Mpa, 60Mpa, etc.; then the temperature is kept for 5 to 12 hours, preferably 7 to 9 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours and the like.
Preferably, the secondary pulverization is carried out by using a vibration mill.
Preferably, the oscillation time of the vibration mill is 10s-5min, preferably 20s-1min, for example, 10s, 15s, 20s, 25s, 30s, 40s, 50s, 1min, 2min, 3min, 4min, 5min, etc.
Preferably, the pressure of the secondary tabletting is 9-60Mpa, preferably 15-30 Mpa, for example, 9Mpa, 12Mpa, 15Mpa, 18Mpa, 20Mpa, 22Mpa, 25Mpa, 28Mpa, 30Mpa, 40Mpa, 50Mpa, 60Mpa, etc.
In the invention, the pressure of the secondary tabletting is regulated to ensure that material particles are in good contact, the too low pressure can cause poor particle contact, so that insufficient reaction is caused, otherwise, too compact material is caused, the growth of crystal grains is restrained, the conductivity is influenced, and in addition, the requirement on a tabletting mould is too high, and the compacted electrolyte sheet is too thin and fragile.
Preferably, the time of the secondary tabletting is 15s-300s, preferably 60s-120s, for example, 15s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 180s, 200s, 300s, etc.
In the invention, by regulating and controlling the time of the secondary tabletting, the material particles are well contacted, the particles become loose again due to the rebound of force when the time is too short, and otherwise, the step time is wasted.
Preferably, the atmosphere of the secondary sintering is any one of air, argon or nitrogen.
In the invention, the secondary sintering can be performed in a muffle furnace, and the upper end and the lower end of the muffle furnace are provided with special tungsten carbide pressure rods, and the pressure can be kept or increased in the sintering process by connecting a tablet press outside. The special tungsten carbide mold can also be made of other materials, such as silicon carbide, boron nitride or silicon nitride, and the like, preferably tungsten carbide.
Preferably, the secondary sintering comprises the following processes: heating to 700-1100deg.C, preferably 850-950 deg.C, such as 700deg.C, 750deg.C, 800deg.C, 850deg.C, 900deg.C, 920 deg.C, 950 deg.C, 1000 deg.C, 1100 deg.C, etc. at a rate of 3-5deg.C/min (such as 3deg.C/min, 3.5 deg.C/min, 4deg.C/min, 4.5 deg.C/min, 5deg.C/min, etc.); the pressure is 0-60Mpa, preferably 30-45Mpa, for example, 2Mpa, 9Mpa, 12Mpa, 15Mpa, 18Mpa, 20Mpa, 22Mpa, 25Mpa, 28Mpa, 30Mpa, 35Mpa, 40Mpa, 45Mpa, 50Mpa, 60Mpa, etc., and the temperature is kept for 6-12h, preferably 8-10h, for example, 6h, 7h, 8h, 9h, 10h, 11h, 12h, etc.
In a second aspect, the present invention provides a NASICON-type solid electrolyte prepared by the method for preparing a NASICON-type solid electrolyte according to the first aspect.
In a third aspect, the present invention provides a secondary battery comprising a positive electrode, a negative electrode and a solid electrolyte comprising the NASICON-type solid electrolyte according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for preparing a NASICON solid electrolyte, which is characterized in that the method of continuously applying pressure in the step heating process is adopted for heating and firing, so that through holes generated in the NASICON solid electrolyte obtained in the traditional preparation method can be effectively reduced, the solid electrolyte is more compact, and the ion conductivity is also improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a LAGP solid electrolyte and a preparation method thereof, wherein the LAGP solid electrolyte comprises the following steps:
5.37g of raw materials of lithium oxide, 50.97g of phosphorus pentoxide, 6.10g of aluminum oxide and 37.56g of germanium oxide are weighed, a 500ml ball milling tank is added, zirconia balls are added according to a proportion, a sealing film is used for sealing, the ball milling speed is set to 380r/min, the ball milling time is 180min, ball milling is alternately carried out in a positive and negative direction every 30min, the middle is stopped for 10min, after ball milling is finished, the materials are crushed by using a vibration mill, the vibration time is 30s, the materials are taken out, the materials are pressed into tablets by using a tablet press and a tungsten carbide tablet grinding tool, the tablet pressing pressure is 20MPa, the tablet pressing time is 120s, the heating speed is set to 4 ℃/min, the temperature is increased to 400 ℃, the material is controlled to 20MPa, the material is taken out after the material is pressed into tablets by using the vibration mill, the tablet press and the tungsten carbide grinding tool are pressed into tablets under the pressure of 20MPa, the temperature is increased to 900 ℃, the material is kept at the temperature for 8h, the time is controlled to be slowly increased, the pressure is controlled to be 1h/2.5MPa, the final pressure is kept at the temperature is 35MPa, and the electrolyte is cooled to the room temperature, and the solid is obtained.
Example 2
The embodiment provides a LATP solid electrolyte and a preparation method thereof, comprising the following steps:
weighing 5.07g of raw materials of lithium oxide, 55.53g of phosphorus pentoxide, 3.99g of aluminum oxide and 35.41g of titanium oxide, adding zirconium oxide balls in proportion after a 500ml ball milling tank, sealing by using a sealing film, setting the ball milling speed to 380r/min, performing ball milling for 180min, alternately performing forward and reverse ball milling every 30min, stopping 10min in the middle, crushing the materials by using a vibration mill after ball milling is finished, vibrating for 30s, taking out material powder, pressing the materials into tablets by using a tablet press and a tungsten carbide tabletting mill, wherein the tabletting pressure is 20MPa, the tabletting time is 120s, the materials are pressed into 20MPa by using a muffle furnace, setting the heating speed to 4 ℃/min, heating to 400 ℃, maintaining for 8h, controlling the material to be 20MPa during the tabletting, taking out, crushing the materials by using the vibration mill, pressing the materials into tablets by using the tablet press and the tungsten carbide tabletting mill under the pressure of 20MPa, sintering in the muffle furnace, heating to 900 ℃, maintaining for 8h, controlling the pressure during the tabletting speed to be 1h/2.5MPa, finally maintaining the pressure to 35MPa, and naturally cooling the solid electrolyte to room temperature.
Example 3
This example differs from example 1 in that the ball milling speed was selected to be 250r/min, and the other is the same as example 1.
Example 4
This example differs from example 1 in that the ball milling time was chosen to be 60 minutes, all other things being equal to example 1.
Example 5
This example differs from example 1 in that the pressure at the time of one compression is 10MPa, and the other is the same as example 1.
Example 6
This example differs from example 1 in that the time for one compression is 30s, all other than that of example 1.
Example 7
The difference between this example and example 1 is that the pressure in the primary sintering is 10MPa, the sintering temperature is 300℃and the temperature is kept for 6 hours, all of which are the same as in example 1.
Example 8
This example differs from example 1 in that the pressure at the time of the secondary compression is 10MPa, and the other is the same as example 1.
Example 9
This example differs from example 1 in that the time for the secondary compression is 30s, all other than that of example 1.
Example 10
The difference between this example and example 1 is that the pressure in the secondary sintering is 20MPa, the sintering temperature is 800 ℃, and the temperature is kept for 6 hours, all of which are the same as in example 1.
Example 11
This example differs from example 2 in that the ball milling speed was selected to be 500r/min, and the other is the same as example 2.
Example 12
This example differs from example 2 in that the ball milling time was chosen to be 1800min, all other things being equal to example 2.
Example 13
This example differs from example 2 in that the pressure at the time of one compression is 60MPa, and the other is the same as example 2.
Example 14
This example differs from example 2 in that the time for one compression is 180s, all other things being equal to example 2.
Example 15
The difference between this example and example 2 is that the pressure in the primary sintering is 70MPa, the sintering temperature is 600 ℃, and the temperature is kept for 14 hours, all of which are the same as in example 2.
Example 16
This example differs from example 2 in that the pressure at the time of the secondary compression is 60MPa, and the other is the same as example 2.
Example 17
This example differs from example 2 in that the time for the secondary compression is 180s, all other things being equal to example 2.
Example 18
The difference between this example and example 2 is that the pressure in the secondary sintering is the final 60MPa, the sintering temperature is 1000 ℃, and the temperature is kept for 14 hours, all of which are the same as in example 2.
Comparative example 1
This comparative example was different from example 1 in that the secondary sintering was not performed with a slow pressure boosting operation, and the secondary sintering was performed by directly pressing the sheet and then sintering the sheet in a muffle furnace, and the other steps were the same as in example 1.
Comparative example 2
This comparative example was different from example 2 in that the secondary sintering was not performed with a slow pressure boosting operation, and the secondary sintering was performed by directly pressing the sheet and then sintering the sheet in a muffle furnace, and the other steps were the same as in example 2.
Test conditions
NASICON type solid electrolytes provided in examples 1 to 18 and comparative examples 1 to 2 were tested as follows:
the electrochemical workstation is adopted, a blocking battery mould is used, and after the baked electrolyte sheet is assembled at room temperature, alternating current impedance detection is carried out. Conductivity calculations were calculated using the following formula:
σ＝(L/S)×R
where σ represents ion conductivity, L is the thickness of the electrolyte sheet, S is the area of the electrolyte sheet, and R is the impedance value measured by the electrolyte sheet.
The test results are shown in table 1:
TABLE 1
As can be seen from the conductivity results in Table 1, the preparation method provided by the invention can improve the ionic conductivity of the solid electrolyte, and specifically, as can be seen from comparison of examples 3-10 and example 1, the ball milling process and sintering process of the LAGP solid electrolyte sheet need to select proper speed, pressure and time, and finally the LAGP solid electrolyte with high conductivity can be obtained.
As can be seen from the comparison of examples 11-18 and example 2, the ball milling process and sintering process of the LATP solid electrolyte sheet are both required to select proper speed, pressure and time, and finally the LATP solid electrolyte with high conductivity can be obtained.
As is clear from comparison of comparative examples 1 and 2 with examples 1 and 2, by slowly increasing the pressure during the secondary sintering, it is possible to ensure that the compactness of the solid electrolyte sheet is improved without being damaged, thereby further improving the ionic conductivity of the electrolyte.
The experiments prove that the solid electrolyte with high conductivity can be obtained by improving the dry ball milling speed, the dry ball milling time, the primary sintering pressure, the primary sintering time, the secondary sintering pressure, the secondary sintering time and the like in the preparation process of the solid electrolyte and improving the secondary sintering method.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method of preparing a NASICON type solid electrolyte, the method comprising the steps of:
carrying out dry ball milling on raw materials corresponding to the NASICON solid electrolyte, crushing once after finishing, tabletting once, and carrying out primary sintering on the material subjected to tabletting once to obtain a precursor material;
and (3) secondarily crushing the precursor material, secondarily tabletting, and secondarily sintering the secondarily tableted material to obtain the NASICON type solid electrolyte.
2. The method of claim 1, wherein the NASICON-type solid electrolyte comprises a LAGP solid electrolyte and/or a LATP solid electrolyte;
preferably, the structural formula of the LAGP solid electrolyte is Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 ；
Preferably, the structural formula of the LATP solid electrolyte is Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 。
3. The method according to claim 1 or 2, wherein the feedstock comprises metal oxides and non-metal oxides;
preferably, the metal oxide comprises any one or a combination of at least two of lithium oxide, aluminum oxide, germanium oxide or titanium oxide;
preferably, the nonmetallic oxide includes any one of phosphorus pentoxide, phosphorus trioxide or a combination of at least two thereof.
4. A method according to any one of claims 1-3, wherein the dry ball milling is carried out at a rate of 200r/min to 500r/min, preferably 300-480r/min;
preferably, the dry ball milling time is 30min-1800min, preferably 120min-1500min;
preferably, the dry ball milling mode is a positive and negative rotation alternating mode, specifically, the conversion is carried out every 0.5h, and the process is stopped for 5-15min, preferably 5-10min.
5. The method of any one of claims 1-4, wherein the primary comminution is comminution using a vibratory mill;
preferably, the oscillation time of the vibration mill is 10s-5min, preferably 20s-1min;
preferably, the pressure of the primary tabletting is 9-60Mpa, preferably 15-30 Mpa;
preferably, the time of the one compression is 15s to 300s, preferably 60s to 120s.
6. The method according to any one of claims 1 to 5, wherein the atmosphere of the primary sintering is any one of air, argon or nitrogen;
preferably, the primary sintering comprises the following processes: heating to 300-500 deg.C, preferably 300-400 deg.C at a rate of 3-5 deg.C/min, and pressure of 0-60MPa, preferably 15-30 MPa; then preserving the heat for 5-12h, preferably 7-9h.
7. The method of any one of claims 1-6, wherein the secondary comminution is comminuting using a vibratory mill;
preferably, the oscillation time of the vibration mill is 10s-5min, preferably 20s-1min;
preferably, the pressure of the secondary tabletting is 9-60Mpa, preferably 15-30 Mpa;
preferably, the time of the secondary tabletting is 15s-300s, preferably 60s-120s.
8. The method of any one of claims 1-7, wherein the atmosphere of the secondary sintering is any one of air, argon, or nitrogen;
preferably, the secondary sintering comprises the following processes: heating to 700-1100deg.C, preferably 850-950 deg.C at a rate of 3-5deg.C/min, maintaining at 0-60MPa, preferably 30-45MPa for 6-12 hr, preferably 8-10 hr.
9. A NASICON-type solid electrolyte, characterized in that the NASICON-type solid electrolyte is produced by the method for producing a NASICON-type solid electrolyte according to any one of claims 1 to 8.
10. A secondary battery, characterized in that the secondary battery comprises a positive electrode, a negative electrode, and a solid electrolyte comprising the NASICON-type solid electrolyte according to claim 9.
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