CN111732433A - Preparation method of garnet type solid electrolyte with controllable particle size - Google Patents
Preparation method of garnet type solid electrolyte with controllable particle size Download PDFInfo
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- CN111732433A CN111732433A CN202010626236.1A CN202010626236A CN111732433A CN 111732433 A CN111732433 A CN 111732433A CN 202010626236 A CN202010626236 A CN 202010626236A CN 111732433 A CN111732433 A CN 111732433A
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- 239000002245 particle Substances 0.000 title claims abstract description 28
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002223 garnet Substances 0.000 title abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 81
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000000227 grinding Methods 0.000 claims abstract description 34
- 238000005303 weighing Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910008035 Li-La-Zr-O Inorganic materials 0.000 description 2
- 229910006268 Li—La—Zr—O Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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Abstract
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a garnet type solid electrolyte with controllable particle size, which comprises the following steps: step 1, respectively weighing 5-20 parts of tantalum-doped lithium lanthanum zirconium oxide powder and 0.5-1 part of dispersing agent, placing the materials in a ball milling tank, and adding 30-120 parts of absolute ethyl alcohol solvent; step 2, weighing grinding balls with different sizes, and placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide subjected to primary ball milling; the ball milling time is 10-15h, the rotating speed is 480-. The preparation method is simple, low in cost and environment-friendly.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a garnet type solid electrolyte with controllable particle size.
Background
The current new energy automobile industry governing department puts forward very high requirements on the performance of the power battery. According to the guidance of 'long-term development planning in automobile industry' and 'energy-saving and new energy automobile technical route diagram', the energy density of the power battery system needs to reach 350Wh/Kg (corresponding to a monomer energy density of 500Wh/Kg) in 2025 + 2030 years so as to meet the cruising mileage requirement of a common electric automobile. However, most of the existing lithium ion battery systems adopt organic liquid electrolyte materials, and have serious safety problems of flammability, explosiveness and the like; on the other hand, in the background of increasing importance of energy density, 350Wh/kg or the limit of the current commercial lithium battery is approached, and the bottleneck of energy density is prominent. The all-solid-state battery adopts solid electrolyte and is not flammable; meanwhile, the solid electrolyte has high mechanical strength, can effectively inhibit the growth of lithium dendrites, and greatly improves the safety performance of the lithium battery. In addition, the all-solid-state lithium battery can adopt metal lithium as a negative electrode (the specific capacity of the metal lithium is close to 10 times of that of a graphite negative electrode), the energy density of the same positive electrode system is expected to be improved by more than 50%, and the energy density of the battery is obviously improved.
Li of garnet structure in a number of solid electrolytes6.5La3Zr1.5Ta0.5O12The garnet type solid electrolyte serving as a ceramic chip assembled battery has the defects of poor mechanical property due to incapability of bearing pressure, and is not beneficial to the mass production of the battery. Researches find that the garnet-type solid electrolyte and the polymer electrolyte are compounded to achieve the purposes of promoting the growth and avoiding the shortages (journal of Power sources195(2010) 4554-4569); and the conductivity is improved more obviously by adding the nano garnet type solid electrolyte than by adding submicron or micron-sized solid electrolyte. In addition, the nano garnet type solid electrolyte has larger specific surface area and more functional groups, and is easy to be linked with the polymer so as to improve the compatibility with the polymer.
Currently, researchers have adopted various methods for preparing a garnet-type solid electrolyte on a nanometer scale, such as: sol-gel methods, molten salt methods, cladding or template growth methods, and the like. However, these methods have complicated operation process, difficult control of particle size, high cost of raw materials required in the preparation process, and complicated process, and are not beneficial to industrialization.
Disclosure of Invention
The invention aims to provide a preparation method of a garnet-type solid electrolyte with controllable particle size, so as to obtain a nanoscale tantalum-doped lithium lanthanum zirconium oxide crystal grain.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention provides a preparation method of a garnet-type solid electrolyte with controllable particle size, which comprises the following steps:
step 1, respectively weighing 5-20 parts of tantalum-doped lithium lanthanum zirconium oxide powder and 0.5-1 part of dispersing agent, placing the materials in a ball milling tank, and adding 30-120 parts of absolute ethyl alcohol solvent;
step 2, weighing grinding balls with different sizes, and placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide subjected to primary ball milling; the ball milling time is 10-15h, and the rotating speed is 480-;
step 3, taking out the grinding balls after the ball milling is finished, and putting the grinding balls with the diameter of 0.2-0.5mm into a ball milling tank for secondary ball milling to prepare the tantalum-doped lithium lanthanum zirconium oxygen slurry, wherein the ball milling time is 8-20h, and the rotating speed is 480 and 500 r/min;
and 4, filtering and drying the tantalum-doped lithium lanthanum zirconium oxide slurry, and crushing and sieving with a 300-500-mesh sieve to obtain the nanoscale tantalum-doped lithium lanthanum zirconium oxide powder.
Preferably, the tantalum-doped lithium lanthanum zirconium oxide is Li6.5La3Zr1.5Ta0.5O12The diameter of the material is 10-30 mu m;
preferably, in step 1: the dispersant is polyethylene oxide or polyethylene glycol, wherein the molecular weight of the polyethylene oxide is 800000-1000000, and the molecular weight of the polyethylene glycol is 200-20000.
Preferably, in step 1: the addition amount of the absolute ethyl alcohol is 6-8 times of the total amount of the tantalum-doped lithium lanthanum zirconium oxide powder.
Preferably, in the step 1-3, the ball mill is a corundum ball mill with a volume of 100-.
Preferably, in the step 4, a 300-500 mesh screen is adopted in the filtering process.
Preferably, in the step 4, the drying is to dry the tantalum-doped lithium lanthanum zirconium oxide slurry to a constant weight at a temperature of 50-70 ℃.
Compared with the prior art, the invention has the beneficial effects that: according to the preparation method of the garnet-type solid electrolyte with the controllable particle size, the surface energy of the tantalum-doped lithium lanthanum zirconium oxygen powder is reduced by using the dispersing agent to limit the aggregation of the tantalum-doped lithium lanthanum zirconium oxygen powder, so that the nanoscale tantalum-doped lithium lanthanum zirconium oxygen powder with uniform size and no impurity phase is obtained. The preparation method is simple, low in cost and environment-friendly.
Drawings
FIG. 1 is an XRD pattern of tantalum-doped lithium lanthanum zirconium oxide powder obtained in example 1 of the present invention;
FIG. 2 is an SEM image of tantalum-doped lithium lanthanum zirconium oxide powder obtained in example 1 of the present invention;
FIG. 3 is a graph showing the distribution of the particle size of tantalum-doped lithium lanthanum zirconium oxide powder obtained in example 1 of the present invention;
FIG. 4 is an XRD pattern of Ta-doped Li-La-Zr-O obtained in example 2 of the present invention;
FIG. 5 is an SEM image of Ta-doped Li-La-Zr-O obtained in example 2 of the present invention;
FIG. 6 is a graph showing the distribution of the tantalum-doped lithium lanthanum zirconium oxide particle size obtained in example 2 of the present invention;
fig. 7 is a graph comparing capacity retention rates of all solid-state lithium batteries assembled by tantalum-doped lithium lanthanum zirconium oxide electrolyte sheets with different particle sizes.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Step 1, respectively weighing 5g of tantalum-doped lithium lanthanum zirconium oxide powder (the diameter is 10-30 mu m), 0.025g of polyethylene oxide (the molecular weight is 1000000) and placing the powder into a ball milling tank, and adding 30mL of absolute ethyl alcohol;
step 2, weighing grinding balls (the diameter is 10-20mm) with different sizes, placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide subjected to primary ball milling; the ball milling time is 12h, and the rotating speed is 500 r/min;
step 3, taking out the grinding balls after the ball milling is finished, putting 50g of the grinding balls with the diameter of 0.3mm into a ball milling tank for secondary ball milling to prepare the tantalum-doped lithium lanthanum zirconium oxide slurry, wherein the ball milling time is 16h, and the rotating speed is 500 r/min;
fig. 1, fig. 2 and fig. 3 are XRD, SEM and particle size distribution diagrams of tantalum-doped lithium lanthanum zirconium oxide prepared by using polyethylene oxide as a dispersant, respectively, from which: the obtained tantalum-doped lithium lanthanum zirconium oxide is pure cubic phase garnet crystal phase, the shape of the crystal grain is similar to a sheet shape, and the crystal size is in the range of 200-400 nm; the particle size distribution shows that the prepared tantalum-doped lithium lanthanum zirconium oxide has the particle size D50 of 189nm and the particle size D90 of 296 nm.
Example 2
Step 1, respectively weighing 5g of tantalum-doped lithium lanthanum zirconium oxide powder (the diameter is 10-30 mu m), 0.025g of polyethylene glycol (the molecular weight is 20000) and placing the powder into a ball milling tank, and adding 30mL of absolute ethyl alcohol;
step 2, weighing grinding balls (the diameter is 10-20mm) with different sizes, placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide after primary ball milling; the ball milling time is 12h, and the rotating speed is 500 r/min;
step 3, taking out the grinding balls after the ball milling is finished, putting 50g of the grinding balls with the diameter of 0.3mm into a ball milling tank for secondary ball milling to prepare the tantalum-doped lithium lanthanum zirconium oxide slurry, wherein the ball milling time is 16h, and the rotating speed is 500 r/min;
fig. 4, fig. 5 and fig. 6 are an XRD chart, an SEM chart and a particle size distribution diagram of the tantalum-doped lithium lanthanum zirconium oxide prepared by using polyethylene glycol as a dispersant, respectively, from which it can be known that: the obtained tantalum-doped lithium lanthanum zirconium oxide is pure cubic phase garnet crystal phase, the shape of crystal grains is similar to sheet-shaped particles, the size of the crystal is in the range of 200-350nm, and the size is uniform; the particle size distribution shows that the prepared tantalum-doped lithium lanthanum zirconium oxide has the particle size D50 of 209nm and the particle size D90 of 323 nm. Fig. 7 is a comparison graph of capacity retention rates of lithium ion solid-state batteries assembled by tantalum-doped lithium lanthanum zirconium oxide electrolyte sheets with two different particle sizes, and it can be seen from the graph that the retention rate is 86% after 160 cycles of cycle by using the nano-scale tantalum-doped lithium lanthanum zirconium oxide electrolyte sheet, which is superior to the solid-state battery assembled by the micro-scale electrolyte sheet (retention rate: 65%).
Example 3
Step 1, respectively weighing 5g of tantalum-doped lithium lanthanum zirconium oxide powder (the diameter is 10-30 mu m), 0.025g of polyethylene glycol (the molecular weight is 20000) and placing the powder into a ball milling tank, and adding 30mL of absolute ethyl alcohol;
step 2, weighing grinding balls (the diameter is 10-20mm) with different sizes, placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide after primary ball milling; the ball milling time is 15h, and the rotating speed is 500 r/min;
step 3, taking out the grinding balls after the ball milling is finished, putting 50g of the grinding balls with the diameter of 0.3mm into a ball milling tank for secondary ball milling to prepare the tantalum-doped lithium lanthanum zirconium oxide slurry, wherein the ball milling time is 16h, and the rotating speed is 500 r/min;
example 4
Step 1, respectively weighing 5g of tantalum-doped lithium lanthanum zirconium oxide powder (the diameter is 10-30 mu m), 0.025g of polyethylene glycol (the molecular weight is 20000) and placing the powder into a ball milling tank, and adding 30mL of absolute ethyl alcohol;
step 2, weighing grinding balls (the diameter is 10-20mm) with different sizes, placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide after primary ball milling; the ball milling time is 15h, and the rotating speed is 500 r/min;
step 3, taking out the grinding balls after the ball milling is finished, putting 75g of the grinding balls with the diameter of 0.3mm into a ball milling tank for secondary ball milling to prepare the tantalum-doped lithium lanthanum zirconium oxide slurry, wherein the ball milling time is 16h, and the rotating speed is 500 r/min;
example 5
Step 1, respectively weighing 5g of tantalum-doped lithium lanthanum zirconium oxide powder (the diameter is 10-30 mu m), 0.025g of polyethylene glycol (the molecular weight is 20000) and placing the powder into a ball milling tank, and adding 30mL of absolute ethyl alcohol;
step 2, weighing grinding balls (the diameter is 10-20mm) with different sizes, placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide after primary ball milling; the ball milling time is 15h, and the rotating speed is 500 r/min;
step 3, taking out the grinding balls after the ball milling is finished, putting 50g of the grinding balls with the diameter of 0.3mm into a ball milling tank for secondary ball milling to prepare the tantalum-doped lithium lanthanum zirconium oxide slurry, wherein the ball milling time is 16h, and the rotating speed is 500 r/min;
example 6
Step 1, respectively weighing 5g of tantalum-doped lithium lanthanum zirconium oxide powder (the diameter is 10-30 mu m), 0.025g of polyethylene glycol (the molecular weight is 20000) and placing the powder into a ball milling tank, and adding 40mL of absolute ethyl alcohol;
step 2, weighing grinding balls (the diameter is 10-20mm) with different sizes, placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide after primary ball milling; the ball milling time is 15h, and the rotating speed is 500 r/min;
step 3, taking out the grinding balls after the ball milling is finished, putting 50g of the grinding balls with the diameter of 0.3mm into a ball milling tank for secondary ball milling to prepare the tantalum-doped lithium lanthanum zirconium oxide slurry, wherein the ball milling time is 16h, and the rotating speed is 500 r/min;
the invention provides a preparation method of a garnet-type solid electrolyte with controllable particle size, which consists of micron-sized tantalum-doped lithium lanthanum zirconium oxide powder, absolute ethyl alcohol and an organic dispersing agent, wherein the raw materials are added into a ball milling tank, and the nano-sized tantalum-doped lithium lanthanum zirconium oxide powder is obtained by simple secondary ball milling technology, ball milling time regulation and control and ball milling rotating speed regulation; the preparation method of the garnet-type solid electrolyte with the controllable particle size, which is provided by the invention, limits the aggregation of the tantalum-doped lithium lanthanum zirconium oxygen powder by reducing the surface energy of the tantalum-doped lithium lanthanum zirconium oxygen powder by using the dispersing agent, so that the nano-scale tantalum-doped lithium lanthanum zirconium oxygen crystal grains with uniform size and no impurity phase are obtained. The preparation method is simple, low in cost and environment-friendly.
While the invention has been described above with reference to an embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the various features of the embodiments disclosed herein may be used in any combination, provided that there is no structural conflict, and the combinations are not exhaustively described in this specification merely for the sake of brevity and conservation of resources. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (7)
1. The preparation method of the garnet-type solid electrolyte with the controllable particle size is characterized by comprising the following steps of:
step 1, respectively weighing 5-20 parts of tantalum-doped lithium lanthanum zirconium oxide powder and 0.5-1 part of dispersing agent, placing the materials in a ball milling tank, and adding 30-120 parts of absolute ethyl alcohol solvent;
step 2, weighing grinding balls with different sizes, and placing the grinding balls in a ball milling tank for ball milling to obtain tantalum-doped lithium lanthanum zirconium oxide subjected to primary ball milling; the ball milling time is 10-15h, and the rotating speed is 480-;
step 3, taking out the grinding balls after the ball milling is finished, and putting the grinding balls with the diameter of 0.2-0.5mm into a ball milling tank for secondary ball milling to prepare the tantalum-doped lithium lanthanum zirconium oxygen slurry, wherein the ball milling time is 8-20h, and the rotating speed is 480 and 500 r/min;
and 4, filtering and drying the tantalum-doped lithium lanthanum zirconium oxide slurry, and crushing and sieving with a 300-500-mesh sieve to obtain the nanoscale tantalum-doped lithium lanthanum zirconium oxide powder.
2. The method according to claim 1, wherein the garnet-type solid electrolyte having a controllable particle size is prepared by: the tantalum-doped lithium lanthanum zirconium oxide is Li6.5La3Zr1.5Ta0.5O12The diameter of the material is 10-30 μm.
3. The method for preparing a garnet-type solid electrolyte having a controlled particle size according to claim 1, wherein the step 1: the dispersant is polyethylene oxide or polyethylene glycol, wherein the molecular weight of the polyethylene oxide is 800000-1000000, and the molecular weight of the polyethylene glycol is 200-20000.
4. The method for preparing a garnet-type solid electrolyte having a controlled particle size according to claim 1, wherein the step 1: the addition amount of the absolute ethyl alcohol is 6-8 times of the total amount of the tantalum-doped lithium lanthanum zirconium oxide powder.
5. The method as claimed in claim 1, wherein in the step 1-3, the ball mill is a 300ml corundum ball mill with 100-.
6. The method as claimed in claim 1, wherein the step 4 is performed by using a 300-500 mesh screen.
7. The method for preparing the garnet-type solid electrolyte with a controlled particle size as claimed in claim 1, wherein the drying in step 4 is performed by drying the tantalum-doped lithium lanthanum zirconium oxide slurry to a constant weight at a temperature of 50-70 ℃.
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