CN115160011A - Method for preparing straight-hole solid-state lithium battery ceramic electrolyte by one-step sintering and application thereof - Google Patents
Method for preparing straight-hole solid-state lithium battery ceramic electrolyte by one-step sintering and application thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 60
- 229910021525 ceramic electrolyte Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005245 sintering Methods 0.000 title claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000008394 flocculating agent Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 2
- 229920000570 polyether Polymers 0.000 claims 2
- 230000009466 transformation Effects 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 11
- 239000012528 membrane Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 238000000498 ball milling Methods 0.000 description 13
- 239000007784 solid electrolyte Substances 0.000 description 11
- 230000007704 transition Effects 0.000 description 9
- 239000004695 Polyether sulfone Substances 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 229920006393 polyether sulfone Polymers 0.000 description 8
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing a straight-hole solid-state lithium battery ceramic electrolyte by one-step sintering, which comprises the following steps: and (1) providing a phase inversion solution for later use. (2) And adding a lithium cathode raw material, lanthanum oxide, titanium oxide and a dispersing agent into the phase conversion solution for grinding to obtain precursor slurry for later use. (3) And pouring the precursor slurry into a mold for molding, adding a flocculating agent on the upper part of the slurry for phase conversion, demolding after the phase conversion is finished, and drying to obtain a blank body with a straight hole structure inside. (4) And heating the blank body to remove the gel, and then calcining to obtain the solid lithium battery ceramic electrolyte with straight holes. The method can prepare the straight-hole ceramic membrane by preparing the blank by the oxide and sintering the blank once, only needs one sintering process, can greatly reduce the energy consumption of ceramic production, shortens the production period of the ceramic membrane, and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of solid electrolyte preparation, in particular to a method for preparing a straight-hole solid lithium battery ceramic electrolyte by one-step sintering and application thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
The traditional liquid electrolyte lithium ion battery has the phenomenon of uneven local ion concentration or electron concentration, so that the local current density is overlarge, and lithium dendrite is easy to generate. With the increase of charging and discharging times, the lithium dendrite grows continuously to puncture the diaphragm, which causes short circuit of the battery and is easy to cause potential safety hazards such as fire and the like. The solid-state battery adopts the solid-state electrolyte to replace the organic electrolyte, so that the potential safety hazard of the traditional lithium ion battery is fundamentally solved, and the collocation of the solid-state electrolyte and the metal lithium cathode is expected to realize higher energy density. Therefore, there is a need to develop a solid electrolyte material having advantages in terms of energy density, cycle life, and safety.
The solid electrolyte is used as an important component of the all-solid-state lithium ion battery, and the inorganic solid electrolyte can keep good electrochemical stability, mechanical property and higher safety characteristic in a wide temperature range. However, the solid electrolyte lacks fluidity, which results in small solid-solid contact area and increased impedance, and this series of interface problems has become a bottleneck for restricting the development of solid batteries.
At present, the preparation method of the solid electrolyte mainly comprises the following two methods: (1) Sintering electrolyte powder by using oxide, manufacturing an electrolyte blank by using a tabletting method, and finally sintering into a ceramic membrane for the second time. Such a solid electrolyte membrane is hard and brittle in the subsequent process, and lithium in the solid electrolyte is lost in each sintering, and manual lithium supplement is required in the sintering process, which also increases the manufacturing cost of the solid electrolyte. (2) The size of the solid electrolyte membrane prepared by tabletting is limited by tabletting equipment, the surface area is small, the contact area of the electrolyte and an electrode material is limited, the load capacity of a positive electrode material is limited, the transmission and application efficiency of lithium ions is influenced, and the capacity of a solid battery is further limited.
Disclosure of Invention
The invention provides a method for preparing a straight-hole solid-state lithium battery ceramic electrolyte by one-step sintering and application thereof. The method prepares the straight-hole ceramic membrane by preparing the blank by the oxide and sintering at one time, can greatly reduce the energy consumption of ceramic production, shortens the production period of the ceramic membrane, and is more suitable for large-scale production. In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect of the invention, a method for preparing a ceramic electrolyte of a straight-hole solid-state lithium battery by one-step sintering is disclosed, which comprises the following steps:
(1) The phase inversion solution is provided for use.
(2) And adding a lithium cathode raw material, lanthanum oxide, titanium oxide and a dispersing agent into the phase conversion solution for grinding to obtain precursor slurry for later use.
(3) And pouring the precursor slurry into a mold for molding, adding a flocculating agent on the upper part of the slurry for phase conversion, demolding after the phase conversion is finished, and drying to obtain a blank body with a straight hole structure inside.
(4) And heating the blank body to remove the gel, and then calcining to obtain the solid lithium battery ceramic electrolyte with straight holes.
Further, in step (1), the phase-change solution comprises: a solution of polyethersulfone in N-methylpyrrolidone, or dimethylsulfoxide. Preferably, the mass fraction of the solute in the conversion solution is 10 to 40wt%.
Further, in the step (2), the mass ratio of the lithium negative electrode raw material, lanthanum oxide, titanium oxide and the dispersing agent is =5 to 30:30 to 40:30 to 40:1 to 5:5 to 30. Alternatively, zrO is used 2 Gallium oxide, yttrium oxide,Strontium oxide, aluminum oxide, taO 5 In place of the titanium oxide.
Further, in the step (2), the lithium negative electrode raw material includes at least one of lithium oxide, lithium carbonate, lithium hydroxide, and the like.
Further, in the step (2), the dispersant comprises polyvinylpyrrolidone (PVP) and the like, and optionally, the molecular weight of the dispersant is 8000 to 1300000.
Further, in the step (2), the grinding time is 24 to 48 hours, so that the raw materials form uniformly mixed slurry.
Further, in the step (3), the flocculant comprises: water, ethanol, and the like. And (3) forming a straight channel structure (namely a straight hole) on the blank by the action of the flocculating agent and the phase conversion solution, wherein the lower end of the channel is positioned on the lower surface of the blank and is in an open shape.
Further, in the step (3), the phase inversion time is 2 to 6 hours.
Further, in the step (3), the drying temperature is 50-100 ℃, and the drying time is 12-24 hours.
Further, in the step (4), the temperature of heating and glue discharging is 300 to 600 ℃, and the time is 60 to 120min.
Further, in the step (4), the calcining temperature is 1100-1500 ℃, and the calcining time is 300-500min. After the preparation of the steps, the preparation of the straight-hole solid-state lithium battery ceramic electrolyte can be realized by one-step sintering.
Further, in the solid-state lithium battery ceramic electrolyte prepared in the step (4), the straight holes contain the positive electrode material, and preferably, the positive electrode material is filled in the straight holes or covers the inner surfaces of the straight holes.
In a second aspect of the invention, the application of the ceramic electrolyte obtained by the method for preparing the straight-hole solid-state lithium battery ceramic electrolyte by one-step sintering in the fields of mobile phones, electric automobiles, aerospace and the like is disclosed.
Compared with the prior art, the invention has the following beneficial effects:
(1) The prepared straight-hole solid-state lithium battery ceramic electrolyte can be filled with more anode materials in unit area, and can better improve the battery capacity.
(2) The method can prepare the straight-hole ceramic membrane by preparing the blank by the oxide and sintering the blank once, only needs one sintering process, can greatly reduce the energy consumption of ceramic production, shortens the production period of the ceramic membrane, and is suitable for large-scale production.
(3) When the prepared straight-hole solid-state lithium battery ceramic electrolyte is applied to lithium battery reaction, the active substance loading capacity per unit area can be effectively improved, the pore canal wall is more favorable for lithium ions to pass through, and the current density per unit area can be greatly improved.
(4) The process can also conveniently prepare various types of ceramic-based solid electrolytes by adjusting the types of the raw materials in the step (2).
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope cross-sectional view of a ceramic electrolyte for a straight-hole solid lithium battery prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope cross-sectional view of a straight-hole solid lithium battery ceramic electrolyte prepared in example 2 of the present invention.
FIG. 3 is a sectional X-ray diffraction pattern of the ceramic electrolyte for a straight-hole solid-state lithium battery prepared in example 1 of the present invention.
Fig. 4 is a charge and discharge curve of an all-solid-state battery prepared from the ceramic electrolyte of the straight-hole solid-state lithium battery prepared in example 1 of the present invention.
Detailed Description
In the following description, further specific details of the invention are set forth in order to provide a thorough understanding of the invention. The terminology used in the description of the invention herein is for the purpose of describing particular advantages and features of the invention only and is not intended to be limiting of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Unless otherwise indicated, the drugs or agents used in the present invention are used according to the instructions of the product or by the conventional methods in the art. The process of the present invention will now be further described with reference to the drawings and detailed description of the specification.
Example 1
A method for preparing a straight-hole solid lithium battery ceramic electrolyte by one-step sintering comprises the following steps:
1. preparing 10 wt% of polyether sulfone N-methyl pyrrolidone solution as a phase transition solution for later use.
2. Weighing the following raw materials: li 2 CO 3 （3.0g）、La 2 O 3 （16.6g）、TiO 2 (16.6 g), PVP (0.72 g, molecular weight 8000) and 16g of phase-transition solution, mixing the raw materials, and placing the mixture in a ball milling device for ball milling for 48 hours to obtain precursor slurry for later use.
3. And (3) adding the slurry obtained in the step (II) into a circular mold with the diameter of 3cm by using 5ml of injection, filling the circular mold with the slurry, covering a wire mesh with the aperture of 150 mu m on the top of the mold, injecting deionized water into the slurry from the top of the mold for phase conversion for 4 hours, demolding after the phase conversion is finished, and drying the blank in an oven at 60 ℃ for 12 hours to obtain a blank with a straight-hole structure inside.
4. Placing the blank body with the straight hole structure inside into a muffle furnace, heating to 400 ℃ at the speed of 2 ℃/min, and then preserving heat for 120min; and then continuously heating to 1280 ℃ at the speed of 2 ℃/min, then preserving the heat for 300min, and naturally cooling to obtain the straight-hole solid-state lithium battery ceramic electrolyte.
Example 2
A method for preparing a straight-hole solid lithium battery ceramic electrolyte by one-step sintering comprises the following steps:
1. and preparing 20 wt% of polyether sulfone N-methyl pyrrolidone solution as a phase transition solution for later use.
2. Weighing the following raw materials: li 2 O（5.0g）+La 2 O 3 （30g）+ ZrO 2 (30g) + PVP (1.0 g, molecular weight 8000) and 5g of phase transition solution, mixing the raw materials, and ball-milling in a ball-milling device for 24 hours to obtain precursor slurry for later use.
3. And (3) adding the slurry obtained in the second step into a circular mould with the diameter of 2cm by using 5ml of injection and filling the mould with the slurry, covering a wire netting with the aperture of 150 mu m on the top of the mould, injecting deionized water into the slurry from the top of the mould for phase conversion for 2 hours, demoulding after finishing, and drying the blank in an oven at 60 ℃ for 12 hours to obtain a blank with a straight hole structure inside.
4. Placing the blank body with the straight hole structure inside into a muffle furnace, heating to 300 ℃ at the speed of 2 ℃/min, and then preserving heat for 120min; and then continuously heating to 1250 ℃ at the speed of 2 ℃/min, then preserving the heat for 400min, and naturally cooling after the completion to obtain the straight-hole solid-state lithium battery ceramic electrolyte.
Example 3
A method for preparing a ceramic electrolyte of a straight-hole solid-state lithium battery by one-step sintering comprises the following steps:
1. preparing 40wt% of polyether sulfone N-methyl pyrrolidone solution as a phase transition solution for later use.
2. Weighing the following raw materials: li 2 O（1.0g）+La 2 O 3 （3.5g）+ Ga 2 O 3 (3.5 g) + PVP (0.3 g, molecular weight 8000) and 2.0g of phase-transition solution, mixing the above raw materials, and ball-milling in a ball-milling device for 30 hours to obtain precursor slurry for later use.
3. And (3) adding the slurry obtained in the second step into a circular mould with the diameter of 2cm by using 5ml of injection, filling the mould with the injection, covering a wire mesh with the aperture of 300 mu m on the top of the mould, injecting ethanol into the slurry from the top of the mould for phase conversion for 4 hours, demoulding after the phase conversion is finished, and drying the blank in an oven at 50 ℃ for 24 hours to obtain a blank with a straight hole structure inside.
4. Placing the blank body with the straight hole structure inside into a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, and then preserving heat for 120min; and then continuously heating to 1100 ℃ at the speed of 5 ℃/min, then preserving the heat for 500min, and naturally cooling after the completion to obtain the straight-hole solid-state lithium battery ceramic electrolyte.
Example 4
A method for preparing a straight-hole solid lithium battery ceramic electrolyte by one-step sintering comprises the following steps:
1. and preparing 30 wt% of polyether sulfone dimethyl sulfoxide solution as a phase conversion solution for later use.
2. Weighing the following raw materials: liOH (3.0 g) + La 2 O 3 （4.0g）+ TaO 5 (4.0 g) + PVP (0.5 g, molecular weight 13000), phase transition solution 3.0g, mixing the above raw materials, placing in a ball mill, ball milling for 30 hours, and obtaining precursor slurry for later use.
3. And (3) adding the slurry obtained in the step two into a circular mold with the diameter of 4cm by using 5ml of injection, filling the mold with the slurry, covering a wire mesh with the aperture of 75um on the top of the mold, injecting ethanol into the slurry from the top of the mold for phase conversion for 6 hours, demolding after the phase conversion is finished, and drying the blank in an oven at 100 ℃ for 12 hours to obtain a blank with a straight-hole structure inside.
4. Placing the blank body with the straight hole structure inside into a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, and then preserving heat for 60min; and then continuously heating to 1500 ℃ at the speed of 5 ℃/min, then preserving the heat for 300min, and naturally cooling after the completion to obtain the straight-hole solid-state lithium battery ceramic electrolyte.
Example 5
A method for preparing a ceramic electrolyte of a straight-hole solid-state lithium battery by one-step sintering comprises the following steps:
1. preparing 15 wt% of polyether sulfone N-methyl pyrrolidone solution as a phase transition solution for later use.
2. Weighing the following raw materials: liOH (2.0 g) + La 2 O 3 （3.0g）+ Al 2 O 3 (3.0 g) + PVP (0.2 g, molecular weight 10000) and 1.0g of phase-change solution, mixing the above raw materials, ball-milling in a ball-milling device for 36 hr to obtain precursor slurryAnd (5) preparing materials for later use.
3. And (3) adding the slurry obtained in the second step into a circular mould with the diameter of 4cm by using 5ml of injection and filling the mould with the slurry, covering a wire netting with the aperture of 75 microns on the top of the mould, injecting water into the slurry from the top of the mould for phase conversion for 3 hours, demoulding after the phase conversion is finished, and drying the blank in an oven at 60 ℃ for 12 hours to obtain a blank with a straight hole structure inside.
4. Placing the blank body with the straight hole structure inside into a muffle furnace, heating to 400 ℃ at the speed of 4 ℃/min, and then preserving heat for 100min; and then continuously heating to 1400 ℃ at the speed of 5 ℃/min, then preserving the heat for 450min, and naturally cooling after the completion to obtain the straight-hole solid-state lithium battery ceramic electrolyte.
Example 6
A method for preparing a ceramic electrolyte of a straight-hole solid-state lithium battery by one-step sintering comprises the following steps:
1. preparing 25 wt% of polyether sulfone N-methyl pyrrolidone solution as a phase transition solution for later use.
2. Weighing the following raw materials: li 2 CO 3 （2.5g）+La 2 O 3 （3.2g）+ Y 2 O 3 (3.6 g), PVP (0.25 g) and 2.5g of phase-transition solution, and the raw materials are mixed and then placed in a ball milling device for ball milling for 36 hours to obtain precursor slurry for later use.
3. And (3) adding the slurry obtained in the second step into a circular mould with the diameter of 1cm by using 5ml of injection and filling, covering a wire netting with the aperture of 120 mu m on the top of the mould, injecting water into the slurry from the top of the mould for phase conversion for 5 hours, demoulding after the phase conversion is finished, and drying the blank in an oven at 60 ℃ for 12 hours to obtain a blank with a straight hole structure inside.
4. Putting the blank body with the straight hole structure inside into a muffle furnace, heating to 350 ℃ at the speed of 3 ℃/min, and then preserving heat for 110min; and then continuously heating to 1300 ℃ at the speed of 5 ℃/min, then preserving the heat for 400min, and naturally cooling after the completion to obtain the straight-hole solid-state lithium battery ceramic electrolyte.
Example 7
A method for preparing a ceramic electrolyte of a straight-hole solid-state lithium battery by one-step sintering comprises the following steps:
1. preparing a 32 wt% polyethersulfone N-methyl pyrrolidone solution as a phase transition solution for later use.
2. Weighing the following raw materials: liOH (1.5 g) + La 2 O 3 (3.4 g) + OSr (3.8 g) + PVP (0.4 g), 3.5g of phase transition solution, mixing the above raw materials, and ball-milling in a ball-milling device for 45 hours to obtain precursor slurry for later use.
3. And (3) adding the slurry obtained in the step two into a circular mold with the diameter of 1cm by using 5ml of injection, filling the circular mold with the slurry, covering a wire mesh with the aperture of 400 mu m on the top of the mold, injecting ethanol into the slurry from the top of the mold for phase conversion for 6 hours, demolding after the phase conversion is finished, and drying the blank in an oven at 60 ℃ for 12 hours to obtain a blank with a straight-hole structure inside.
4. Placing the blank body with the straight hole structure inside into a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, and then preserving heat for 90min; and then continuously heating to 1200 ℃ at the speed of 5 ℃/min, then preserving the heat for 450min, and naturally cooling after the completion to obtain the straight-hole solid-state lithium battery ceramic electrolyte.
Performance testing：
Fig. 1 and 2 are cross-sectional scanning views (SEM) of the ceramic electrolytes of the straight-hole solid-state lithium batteries prepared in examples 1 and 2, respectively, and it can be seen that the ceramic electrolytes have a straight channel structure (i.e., straight holes) inside, and the lower ends of the channels are open at the lower surface of the green body, so that the cathode material can be filled into the channels from the lower ports of the channels, and the structure can load the ceramic electrolytes with more cathode material relative to the surface coating, thereby better improving the battery capacity.
FIG. 3 is a sectional X-ray diffraction pattern of the ceramic electrolyte for a straight-hole solid state lithium battery prepared in example 1. It can be seen that the ceramic electrolyte prepared in this example had a composition of Li 0.34 La 0.56 TiO 3 。
Fig. 4 is a charge and discharge curve of an all-solid-state battery prepared from the ceramic electrolyte for a straight-hole solid-state lithium battery prepared in example 1. It can be seen that: the all-solid-state battery prepared by the ceramic electrolyte of the straight-hole solid-state lithium battery is stable in charge and discharge under repeated cycles and has large charge and discharge electric quantity.
The above description is only illustrative of several embodiments of the present invention and should not be taken as limiting the scope of the invention. It should be noted that other persons skilled in the art can make modifications, substitutions and improvements without departing from the spirit and scope of the present invention, and these are all within the protection scope of the present invention. Therefore, the scope of the invention should be determined from the description and claims.
Claims (10)
1. A method for preparing a ceramic electrolyte of a straight-hole solid lithium battery by one-step sintering is characterized by comprising the following steps:
(1) Providing a phase conversion solution for later use;
(2) Adding a lithium cathode raw material, lanthanum oxide, titanium oxide and a dispersing agent into the phase conversion solution for grinding to obtain precursor slurry for later use;
(3) Pouring the precursor slurry into a mold for molding, adding a flocculating agent on the upper part of the slurry for phase conversion, demolding after the phase conversion is finished, and drying to obtain a blank body with a straight hole structure inside;
(4) And heating the blank body for removing the gel, and then calcining to obtain the solid-state lithium battery ceramic electrolyte with straight holes.
2. The method for preparing a ceramic electrolyte of a straight-hole solid lithium battery by one-step sintering according to claim 1, wherein in the step (1), the phase-conversion solution comprises: the polyether sulfone-dissolved N-methyl pyrrolidone solution and the polyether sulfone-dissolved dimethyl sulfoxide; preferably, the mass fraction of the solute in the conversion solution is 10 to 40wt%.
3. The method for preparing the ceramic electrolyte of the straight-hole solid lithium battery in one-step sintering according to claim 1, wherein in the step (2), the mass ratio of the lithium cathode raw material, lanthanum oxide, titanium oxide and a dispersing agent is =5 to 30:30 to 40:30 to 40:1 to 5:5 to 30 percent;
preferably, zrO is used 2 Gallium oxide, yttrium oxide, strontium oxide, aluminum oxide, taO 5 Any one of them is substituted for the titanium oxide.
4. The method for preparing the ceramic electrolyte of the straight-hole solid lithium battery through one-step sintering according to claim 1, wherein in the step (2), the lithium anode raw material comprises at least one of lithium oxide, lithium carbonate and lithium hydroxide;
preferably, in the step (2), the dispersant comprises polyvinylpyrrolidone, and more preferably, the polyvinylpyrrolidone has a molecular weight of 8000 to 1300000;
preferably, in the step (2), the grinding time is 24 to 48 hours.
5. The method for preparing the ceramic electrolyte of the straight-hole solid lithium battery by one-step sintering according to claim 1, wherein in the step (3), the flocculating agent comprises the following steps: water and ethanol.
6. The method for preparing the ceramic electrolyte of the straight-hole solid lithium battery by one-step sintering according to any one of claims 1 to 5, wherein in the step (3), the phase transformation time is 2 to 6 hours;
preferably, in the step (3), the drying temperature is 50 to 100 ℃ and the drying time is 12 to 24 hours.
7. The method for preparing the ceramic electrolyte of the straight-hole solid lithium battery by one-step sintering according to any one of claims 1 to 5, wherein in the step (4), the temperature for heating and glue discharging is 300 to 600 ℃ and the time is 60 to 120min.
8. The method for preparing the ceramic electrolyte of the straight-hole solid lithium battery by one-step sintering according to any one of claims 1 to 5, wherein in the step (4), the calcining temperature is 1100 to 1500 ℃ and the calcining time is 300 to 500min.
9. The method for preparing a ceramic electrolyte of a straight-hole solid lithium battery by one-step sintering according to any one of claims 1 to 5, wherein the ceramic electrolyte of the solid lithium battery prepared in the step (4) contains a positive electrode material in straight holes; preferably, the positive electrode material fills the straight hole or covers the inner surface of the straight hole.
10. The use of the ceramic electrolyte obtained by the method for preparing the straight-hole solid-state lithium battery ceramic electrolyte according to any one of claims 1 to 9 through one-step sintering in the fields of mobile phones, electric automobiles or aerospace.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406118A (en) * | 2015-12-30 | 2016-03-16 | 哈尔滨工业大学 | Ceramic solid electrolyte and preparation method thereof |
| CN105470568A (en) * | 2016-01-11 | 2016-04-06 | 中国科学技术大学 | Solid lithium ion electrolyte and preparation method therefor |
| CN110372367A (en) * | 2019-07-12 | 2019-10-25 | 成都新柯力化工科技有限公司 | A kind of lithium battery high-ductility ceramic solid electrolyte material and preparation method |
| CN112436171A (en) * | 2020-11-24 | 2021-03-02 | 济南大学 | Solid electrolyte support body and preparation method and application thereof |
| CN113372110A (en) * | 2021-05-28 | 2021-09-10 | 北京高压科学研究中心 | Method for preparing perovskite type solid electrolyte lanthanum lithium titanate based on high-temperature and high-pressure synthesis |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406118A (en) * | 2015-12-30 | 2016-03-16 | 哈尔滨工业大学 | Ceramic solid electrolyte and preparation method thereof |
| CN105470568A (en) * | 2016-01-11 | 2016-04-06 | 中国科学技术大学 | Solid lithium ion electrolyte and preparation method therefor |
| CN110372367A (en) * | 2019-07-12 | 2019-10-25 | 成都新柯力化工科技有限公司 | A kind of lithium battery high-ductility ceramic solid electrolyte material and preparation method |
| CN112436171A (en) * | 2020-11-24 | 2021-03-02 | 济南大学 | Solid electrolyte support body and preparation method and application thereof |
| CN113372110A (en) * | 2021-05-28 | 2021-09-10 | 北京高压科学研究中心 | Method for preparing perovskite type solid electrolyte lanthanum lithium titanate based on high-temperature and high-pressure synthesis |
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