CN114621010A - Solid electrolyte of lithium ion battery and preparation method thereof - Google Patents
Solid electrolyte of lithium ion battery and preparation method thereof Download PDFInfo
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- CN114621010A CN114621010A CN202110443690.8A CN202110443690A CN114621010A CN 114621010 A CN114621010 A CN 114621010A CN 202110443690 A CN202110443690 A CN 202110443690A CN 114621010 A CN114621010 A CN 114621010A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 81
- 238000005245 sintering Methods 0.000 claims abstract description 51
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 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 40
- 238000001035 drying Methods 0.000 claims abstract description 39
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 15
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 9
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 7
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001195 gallium oxide Inorganic materials 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 98
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002223 garnet Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 235000012431 wafers Nutrition 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 238000007731 hot pressing Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000005070 sampling Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 7
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- -1 hydrotalcite modified lithium lanthanum zirconium oxygen Chemical class 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention provides a lithium ion battery solid electrolyte and a preparation method thereof, comprising the following steps: pre-sintering lanthanum oxide, ball-milling twice, drying twice, tabletting, sintering and sampling; lithium carbonate, lanthanum oxide, zirconium dioxide, gallium oxide and tantalum pentoxide are mixed and stirred, a sintering curve is divided into four sections, three sections of heating curves and one section of cooling curve are included, and three sections of heating and cooling rates are limited to adjust the sintering temperature; the doped and modified garnet-type solid electrolyte belongs to a cubic phase, has better conductivity at room temperature, and has higher ionic conductivity.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a lithium ion battery solid electrolyte and a preparation method thereof.
Background
At present, commercial lithium ion batteries mainly adopt liquid electrolyte, and in the use process of the lithium ion batteries, because the uneven lithium dendrite growth that leads to of lithium ion spatial distribution, the battery diaphragm is punctured to the lithium dendrite that grows out, causes the leakage of liquid electrolyte, because the liquid electrolyte who uses is mostly high-molecular polymer, the liquid electrolyte who reveals takes place spontaneous combustion easily at high temperature, leads to the overheated inefficacy of lithium ion batteries, leads to the lithium ion batteries even to catch fire, explode.
In the prior art, chinese patent "an oxide solid electrolyte material and a preparation method and application thereof", application No. 202010157145.8, discloses that solid electrolyte powder comprises lithium oxide, lanthanum oxide, zirconium dioxide, and tantalum oxide, and is subjected to one-time dry grinding, wherein the one-time dry grinding results in insufficient grinding of powder raw materials, uneven distribution of powder particles, and also causes uneven conductivity of the electrolyte, and overheating of the battery.
Chinese patent "a hydrotalcite modified lithium lanthanum zirconium oxygen solid electrolyte and its preparation method", application No. 201811418076.0, lithium lanthanum zirconium oxygen powder utilizes sol-gel method to prepare, and the crystalline phase is the tetragonal phase, and the position of lithium is fully occupied by lithium in the tetragonal phase, and the geometry space that lithium ion moved is less, and lithium ion transmission is very difficult, leads to lithium lanthanum zirconium oxygen garnet type solid electrolyte's electric conductivity very poor under the room temperature, and its ionic conductivity is less.
Disclosure of Invention
Therefore, the invention provides a preparation method of a lithium ion battery solid electrolyte to solve the problems of overheating of a lithium ion battery and the like caused by poor conductivity of a lithium lanthanum zirconium oxygen garnet type solid electrolyte.
The technical scheme of the invention is realized as follows:
the solid electrolyte of the lithium ion battery is prepared by mixing lithium carbonate, lanthanum oxide, zirconium dioxide, gallium oxide and tantalum pentoxide at a molar ratio of 115-127: 58-62: 1-5: 10, wherein the preferred molar ratio is 121:60:60:3: 10. Lithium carbonate, lanthanum oxide, zirconium dioxide, gallium oxide and pentaThe chemical formula of the tantalum oxide is respectively Li2CO3、La2O3、ZrO2、Ga2O3、Ta2O5。
Further, the preparation method of the solid electrolyte of the lithium ion battery comprises the following steps:
s1, lanthanum oxide presintering: weighing La2O3Sintering powder by using an alumina crucible, wherein the sintering conditions are as follows: the heating rate is 2-5 ℃/min, the temperature is increased to 800-1000 ℃, and the heat preservation time is 8-12 h;
s2, first ball milling: pre-sintering La obtained in the step S12O3With Li2CO3、ZrO2、Ga2O3、Ta2O5Mixing and stirring to obtain a powder raw material, adding zirconium dioxide balls, pouring into a ball milling tank, pouring an isopropanol solution until the powder raw material and the zirconium dioxide balls are completely submerged, and carrying out ball milling for 10-15 h at the ball milling speed of 150-300 rpm;
s3, primary drying: after the first ball milling is finished, putting the obtained slurry into a drying oven at 100-200 ℃ for drying for 20-30 h to obtain powder I;
s4, pre-sintering: take out above-mentioned powder I, pour into the alumina crucible, the compaction reduces the interval between the powder granule to improve sintering effect, put into the muffle furnace and carry out presintering, sintering condition: heating to 900-1000 ℃ at a heating rate of 1-4 ℃/min, preserving heat for 3-8 h, and cooling to obtain powder II;
s5, secondary ball milling: taking out the powder II of the S4, adding zirconium dioxide balls, pouring into a ball milling tank, pouring an isopropanol solution until the powder raw materials and the zirconium dioxide balls are completely submerged, and carrying out ball milling for 10-15 h at the ball milling speed of 150-300 rpm;
s6, drying for the second time: after the second ball milling is finished, putting the obtained slurry into a drying oven at 100-200 ℃ for drying for 20-30 h to obtain doped and modified garnet-type solid electrolyte powder;
s7, tabletting: adding a polyvinyl alcohol solution into the doped and modified garnet-type solid electrolyte powder, stirring, drying for 3-8 min, taking out the dried powder, sieving by using a 40-mesh and 100-mesh combined screen, collecting the powder, carrying out hot pressing at normal temperature, and respectively pressing into a wafer and a gasket;
s8, sintering: putting the pressed round pieces into a platinum crucible, vertically stacking, placing a gasket on the uppermost layer, laying modified garnet-type solid electrolyte mother powder between the pieces, placing the filled platinum crucible in a muffle furnace, sintering at four stages, heating to 80-120 ℃ at a heating rate of 2-4 ℃/min for 1-3 h at the first stage, heating to 400-500 ℃ at a heating rate of 2-4 ℃/min at the second stage, heating to 1050-1150 ℃ at a heating rate of 1-3 ℃/min at the third stage, heating for 10-20 h at the fourth stage, cooling to 20-30 ℃ at a cooling rate of 3-8 ℃/min, taking out the pieces after sintering, and storing in a vacuum drying box.
Further, the zirconium dioxide balls are divided into large balls and small balls, the diameter of each large ball is 8-12 mm, the diameter of each small ball is 3-6 mm, and the mass ratio of the powder raw materials to the large balls to the small balls is 1: 1-3: 3-5, preferably 1:2: 4.
Further, the ball milling methods in S2 and S5 are all ball milling for 1 hour, pause for 0.5 hour, change the ball milling rotation direction of the ball mill, and then continue ball milling.
Further, the polyvinyl alcohol solution in the S7 tabletting is prepared: according to the mass ratio of 1: 8-15, weighing polyvinyl alcohol and deionized water, pouring the polyvinyl alcohol into the deionized water, heating the deionized water to 80-120 ℃, and stirring by using a magnetic stirrer until the polyvinyl alcohol is completely dissolved in the deionized water to obtain a polyvinyl alcohol solution.
Further, the sintering in the S8 is divided into four sections, wherein in the first section, the temperature is raised to 100 ℃ at 25 ℃, the heating rate is 3 ℃/min, the temperature is kept for 2h, in the second section, the temperature is raised to 450 ℃, the heating rate is 3 ℃/min, the temperature is kept for 2h, in the third section, the temperature is raised to 1100 ℃, the heating rate is 1 ℃/min, the temperature is kept for 15h, in the fourth section, the temperature is lowered to 25 ℃, and the temperature is lowered at 5 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
among the different types of solid electrolytes, the lithium lanthanum zirconium oxygen garnet-type solid electrolyte has many advantages, electricityThe chemical window is large, the ionic conductivity is high, and the chemical general formula is Li7La3Zr2O12On the basis of the solid electrolyte, Ga element and Ta element are introduced by doping, the doped Ga element replaces Li element, the doped Ta element replaces Zr element, and the chemical general formula of the doped Ta element is Li6.05Ga0.15La3Zr1.5Ta0.5O12. Compared with undoped garnet solid electrolyte, the doped modified garnet solid electrolyte belongs to cubic phase, has better conductivity at room temperature, and has larger ionic conductivity.
Drawings
FIG. 1 shows a garnet-type solid electrolyte Li6.05Ga0.15La3Zr1.5Ta0.5O12The precursor in the figure is the doped and modified garnet-type solid electrolyte powder obtained in step S6.
FIG. 2 shows garnet-type solid electrolytes Li prepared in examples 1, 2 and 3 at room temperature6.05Ga0.15La3Zr1.5Ta0.5O12EIS map of (a).
FIG. 3 garnet-type solid electrolytes Li prepared in examples 3, 4 and 5 at room temperature6.05Ga0.15La3Zr1.5Ta0.5O12、Li6.35Ga0.05La3Zr1.5Ta0.5O12、Li5.75Ga0.25La3Zr1.5Ta0.5O12EIS map of (a).
FIG. 4 shows a garnet-type solid electrolyte Li prepared in example 36.05Ga0.15La3Zr1.5Ta0.5O12With Li7La3Zr2O12XRD pattern of (a).
FIG. 5 shows a garnet-type solid electrolyte Li prepared in example 36.05Ga0.15La3Zr1.5Ta0.5O12With Li7La3Zr2O12SEM image of (d).
FIG. 6 shows a lower garnet-type solid electrolyte Li prepared in example 3 at 65 ℃ C6.05Ga0.15La3Zr1.5Ta0.5O12With Li7La3Zr2O12EIS map of (a).
FIG. 7 shows a garnet-type solid electrolyte Li6.05Ga0.15La3Zr1.5Ta0.5O12EIS profiles at different temperatures.
FIG. 8 shows a garnet-type solid electrolyte Li6.05Ga0.15La3Zr1.5Ta0.5O12The Arrhenius fitting spectrum test chart of the relationship between the ionic conductivity and the temperature.
Detailed Description
In order that the technical contents of the invention may be better understood, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
Example 1
A preparation method of a solid electrolyte of a lithium ion battery comprises the following steps:
s1, lanthanum oxide presintering: weighing La2O3Sintering powder in an alumina crucible under the following sintering conditions: the heating rate is 2 ℃/min, the temperature is increased to 800 ℃, and the heat preservation time is 8 h;
s2, first ball milling: li with a molar ratio of 121:60:60:1:10 is used2CO3、La2O3、ZrO2、Ga2O3、Ta2O5Mixing and stirring to obtain a powder raw material, adding zirconium dioxide balls, pouring into a ball milling tank, pouring an isopropanol solution until the powder raw material and the zirconium dioxide balls are completely submerged, and carrying out ball milling for 10 hours at the ball milling speed of 150 rpm; the zirconium dioxide balls are divided into large balls and small balls, and the mass ratio of the powder raw materials to the large balls to the small balls is 1:2: 4; the ball milling method comprises ball milling for 1h, suspending for 0.5h, continuing ball milling, andchanging the ball milling rotation direction of the ball mill;
s3, primary drying: after the first ball milling is finished, putting the obtained slurry into a drying oven at 100 ℃ for drying for 20 hours to obtain powder I;
s4, pre-sintering: taking out the powder I, pouring the powder I into an alumina crucible, compacting the powder I by using a grinding rod, and then putting the powder I into a muffle furnace for presintering, wherein the sintering conditions are as follows: heating to 900 ℃ at the heating rate of 1 ℃/min, preserving heat for 3 hours, and cooling to obtain powder II;
s5, secondary ball milling: taking out the powder II of the S4, adding zirconium dioxide balls, pouring into a ball milling tank, pouring isopropanol solution until the powder raw materials and the zirconium dioxide balls are completely submerged, carrying out ball milling for 10 hours at the ball milling speed of 150rpm, pausing for 0.5 hour for each ball milling 1 hour, and changing the ball milling rotation direction of the ball mill and then continuing ball milling;
s6, drying for the second time: after the second ball milling is finished, putting the obtained slurry into a drying oven at 100 ℃ for drying for 20 hours to obtain doped and modified garnet type solid electrolyte powder;
s7, tabletting: according to the mass ratio of 1: weighing polyvinyl alcohol and deionized water, pouring the polyvinyl alcohol into the deionized water, heating the polyvinyl alcohol to 80 ℃, stirring the polyvinyl alcohol by using a magnetic stirrer until the polyvinyl alcohol is completely dissolved in the deionized water to obtain a binder PVA, adding 10 wt% of PVA into the garnet-type solid electrolyte powder after doping modification, uniformly stirring the mixture, putting the mixture into a drying box at 100 ℃, drying the mixture for 3min, taking out the dried powder, sieving the powder by using a 40-mesh and 100-mesh combined sieve, collecting the powder, weighing 0.7g of the powder, hot-pressing the powder at normal temperature into a wafer, weighing 2.4g of the powder, and hot-pressing the powder at normal temperature into a gasket; and (3) normal-temperature hot-pressing conditions: carrying out normal-temperature hot pressing by using a three-petal mold with the diameter of 15mm, applying a vertical pressure of 28MPa, and keeping the pressure for 3 min;
s8, sintering: putting the pressed wafer into a platinum crucible, vertically stacking, placing a gasket on the uppermost layer, laying modified garnet-type solid electrolyte powder between the wafers, placing the filled platinum crucible into a muffle furnace, dividing a sintering curve into four sections, wherein the sintering curve comprises three sections of heating curves and one section of cooling curve, the first section is heated to 80 ℃ at the temperature of 20 ℃, the heating rate is 2 ℃/min, and the temperature is kept for 1h, the second section is heated to 400 ℃ at the temperature of 80 ℃, the heating rate is 2 ℃/min, the temperature is kept for 1h, the third section is heated to 1050 ℃ at the temperature of 400 ℃, the heating rate is 1 ℃/min, the temperature is kept for 10h, the fourth section is cooled to 20 ℃ at the temperature of 1050 ℃, the cooling rate is 3 ℃/min, after sintering is finished, taking out the wafers, and placing the wafers in a vacuum drying box for storage.
Example 2
A preparation method of a solid electrolyte of a lithium ion battery comprises the following steps:
s1, lanthanum oxide presintering: weighing La2O3Sintering powder in an alumina crucible under the following sintering conditions: the heating rate is 5 ℃/min, the temperature is raised to 1000 ℃, and the heat preservation time is 12 h;
s2, first ball milling: li with a molar ratio of 121:60:60:3:10 is used2CO3、La2O3、ZrO2、Ga2O3、Ta2O5Mixing and stirring to obtain a powder raw material, adding zirconium dioxide balls, pouring into a ball milling tank, pouring an isopropanol solution until the powder raw material and the zirconium dioxide balls are completely submerged, and carrying out ball milling for 15 hours at the ball milling speed of 300 rpm; the zirconium dioxide balls are divided into large balls and small balls, and the mass ratio of the powder raw materials to the large balls to the small balls is 1:2: 4; the ball milling method comprises the steps of ball milling for 1 hour, pausing for 0.5 hour, continuing ball milling, and changing the ball milling rotation direction of the ball mill;
s3, primary drying: after the first ball milling is finished, putting the obtained slurry into a drying oven at 100 ℃ for drying for 20 hours to obtain powder I;
s4, pre-sintering: taking out the powder I, pouring the powder I into an alumina crucible, compacting the powder I by using a grinding rod, and then putting the powder I into a muffle furnace for presintering, wherein the sintering conditions are as follows: heating to 1000 ℃ at a heating rate of 4 ℃/min, keeping the temperature for 8 hours, and cooling to 20 ℃ along with the furnace to obtain powder II;
s5, secondary ball milling: taking out the powder II of the S4, adding zirconium dioxide balls, pouring into a ball milling tank, pouring isopropanol solution until the powder raw materials and the zirconium dioxide balls are completely submerged, carrying out ball milling for 15 hours at the ball milling speed of 300rpm, pausing for 0.5 hour every time the ball milling is carried out for 1 hour, and continuing ball milling after changing the ball milling rotation direction of the ball mill;
s6, drying for the second time: after the second ball milling is finished, putting the obtained slurry into a drying oven at 200 ℃ for drying for 30h to obtain doped and modified garnet type solid electrolyte powder;
s7, tabletting: according to the mass ratio of 1: 15, weighing polyvinyl alcohol and deionized water, pouring the polyvinyl alcohol into the deionized water, heating the deionized water to 120 ℃, stirring by using a magnetic stirrer until the polyvinyl alcohol is completely dissolved in the deionized water to obtain a binder PVA, adding 20 wt% of PVA into the garnet-type solid electrolyte powder after doping modification, uniformly stirring, putting into a drying box at 150 ℃, drying for 8min, taking out the dried powder, sieving by using a 40-mesh and 100-mesh combined screen, collecting the powder, weighing 0.7g of the powder, hot-pressing the powder at normal temperature into a wafer, weighing 2.4g of the powder, hot-pressing the powder at normal temperature into a gasket, and hot-pressing at normal temperature: carrying out normal-temperature hot pressing by using a three-petal mold with the diameter of 15mm, applying a vertical pressure of 28MPa, and keeping the pressure for 5 min;
s8, sintering: putting the pressed wafer into a platinum crucible, vertically stacking, placing a gasket on the uppermost layer, laying modified garnet-type solid electrolyte powder between the wafers, placing the filled platinum crucible into a muffle furnace, dividing a sintering curve into four sections, wherein the sintering curve comprises three sections of heating curves and one section of cooling curves, the first section is heated to 30-120 ℃, the heating rate is 4 ℃/min, the heat is preserved for 3h, the second section is heated to 500 ℃, the heating rate is 4 ℃/min, the heat is preserved for 3h, the third section is heated to 1150 ℃, the heating rate is 3 ℃/min, the heat is preserved for 20h, the fourth section is cooled to 30 ℃ at 1150 ℃, and the cooling rate is 8 ℃/min;
s9, sampling: after sintering, the pieces were taken out, bottled in glass bottles, cotton was stoppered at the bottle mouth, and stored in a vacuum oven at 110 ℃.
Example 3
A preparation method of a solid electrolyte of a lithium ion battery comprises the following steps:
s1, lanthanum oxide presintering: weighing lanthanum oxide powder, sintering by using an alumina crucible, wherein the sintering conditions are as follows: the heating rate is 3 ℃/min, the temperature is increased to 900 ℃, and the heat preservation time is 10 h;
s2, first ball milling: li with a molar ratio of 121:60:60:3:10 is adopted2CO3、La2O3、ZrO2、Ga2O3、Ta2O5Mixing and stirring to obtain a powder raw material, adding zirconium dioxide balls, pouring into a ball milling tank, pouring an isopropanol solution until the powder raw material and the zirconium dioxide balls are completely submerged, and carrying out ball milling for 12 hours at a ball milling speed of 200 rpm; the zirconium dioxide balls are divided into large balls and small balls, and the mass ratio of the powder raw materials to the large balls to the small balls is 1:2: 4; the ball milling method comprises the steps of ball milling for 1 hour, pausing for 0.5 hour, continuing ball milling, and changing the ball milling rotation direction of the ball mill;
s3, primary drying: after the first ball milling is finished, putting the obtained slurry into a 120 ℃ drying oven for drying for 24 hours to obtain powder I;
s4, pre-sintering: taking out the powder I, pouring the powder I into an alumina crucible, compacting the powder I by using a grinding rod, and then putting the powder I into a muffle furnace for presintering, wherein the sintering conditions are as follows: heating to 950 ℃ at a heating rate of 3 ℃/min, preserving heat for 6h, and cooling to 20 ℃ along with the furnace to obtain powder II;
s5, secondary ball milling: taking out the powder II of the S4, adding zirconium dioxide balls into the powder II, pouring the mixture into a ball milling tank, pouring isopropanol solution into the ball milling tank until the powder raw materials and the zirconium dioxide balls are completely submerged, carrying out ball milling for 12 hours at the ball milling speed of 200rpm, pausing for 0.5 hour for each ball milling time, changing the ball milling rotation direction of the ball mill, and continuing ball milling;
s6, drying for the second time: after the second ball milling is finished, putting the obtained slurry into a drying oven at 120 ℃ for drying for 24 hours to obtain doped and modified garnet-type solid electrolyte powder;
s7, tabletting: according to the mass ratio of 1: weighing polyvinyl alcohol and deionized water, pouring the polyvinyl alcohol into the deionized water, heating the polyvinyl alcohol to 100 ℃, stirring the polyvinyl alcohol by using a magnetic stirrer until the polyvinyl alcohol is completely dissolved in the deionized water to obtain a binder PVA, adding 15 wt% of PVA into the garnet-type solid electrolyte powder after doping modification, uniformly stirring the mixture, putting the mixture into a drying box with the temperature of 120 ℃, drying the mixture for 5min, taking the dried powder out, sieving the powder by using a 40-mesh and 100-mesh combined sieve, collecting the powder, performing normal-temperature hot pressing by using a three-petal mold with the diameter of 15mm, and performing normal-temperature hot pressing under the conditions of normal-temperature hot pressing: 0.7 g/tablet, applying 28MPa of vertical pressure, keeping the pressure for 3min, weighing 2.4g of powder under the same tabletting condition, and pressing into a gasket;
s8, sintering: putting the pressed wafer into a platinum crucible, vertically stacking, paving doped and modified garnet type solid electrolyte powder between wafers, putting the loaded platinum crucible into a muffle furnace, dividing a sintering curve into four sections, wherein the sintering curve comprises three sections of heating curves and one section of cooling curve, the first section is 25-100 ℃, the heating rate is 3 ℃/min, the heat preservation is 2h, the second section is 100-450 ℃, the heating rate is 3 ℃/min, the heat preservation is 2h, the third section is 450 ℃, the heating rate is 1 ℃/min, the heat preservation is 15h, the fourth section is 1100 ℃, the temperature is reduced to 25 ℃, and the cooling rate is 5 ℃/min;
s9, sampling: after sintering, the pieces were taken out, bottled in glass bottles, cotton was stoppered at the bottle mouth, and stored in a vacuum oven at 110 ℃.
Example 4
This example differs from example 3 in that the Li2CO3、La2O3、ZrO2、Ga2O3、Ta2O5In a molar ratio of 127:60:60:1:10, and the other steps and process parameters were the same as in example 3.
Example 5
This example differs from example 3 in that the Li2CO3、La2O3、ZrO2、Ga2O3、Ta2O5In a molar ratio of 115:60:60:5:10, and the other steps and process parameters were the same as in example 3.
Comparative example 1
This comparative example differs from example 3 in that a commercially available undoped modified garnet-type solid electrolyte Li was used7La3Zr2O12The operation steps S7 to S9 are the same.
First, performance test
To implementationExample 1-3 Dual-doped modified garnet-type solid electrolyte Li6.05Ga0.15La3Zr1.5Ta0.5O12Surface polishing, silver paste coating, blocking electrode formation, measurement of impedance of garnet-type solid electrolyte by EIS, calculation of ionic conductivity of the garnet-type solid electrolyte by Zview fitting, as shown in FIG. 2, example 3, garnet-type solid electrolyte Li at room temperature6.05Ga0.15La3Zr1.5Ta0.5O12Has an impedance of 295.49 omega and an ionic conductivity of 2.87X 10-4S/cm, impedance of 8200. omega. in example 1, and ionic conductivity of 1.04X 10-5S/cm, the impedance of example 2 was 3737. omega. and the ionic conductivity thereof was 2.27X 10-5S/cm, which illustrates that the garnet-type solid electrolyte prepared by the process parameters of example 3 of the present invention has the best conductivity, because the specific sintering temperature is favorable for eliminating the grain boundary resistance in the garnet-type solid electrolyte, but the sintering temperature is not reached, which may affect the elimination of the grain boundary resistance, and the too high sintering temperature may cause the garnet-type solid electrolyte to grow too large to destroy the uniformity of the structure, to sum up, the selection of the proper sintering temperature in example 3 is favorable for obtaining the garnet-type solid electrolyte with the best electrochemical performance.
Example 3 to 5, the garnet-type solid electrolyte Li prepared by double doping modification6.05Ga0.15La3Zr1.5Ta0.5O12、Li6.35Ga0.05La3Zr1.5Ta0.5O12、Li5.75Ga0.25La3Zr1.5Ta0.5O12Example 3 garnet-type solid electrolyte Li at room temperature, as shown in FIG. 36.05Ga0.15La3Zr1.5Ta0.5O12Has an impedance of 295.49 Ω and an ionic conductivity of 2.87X 10-4S/cm, example 4 garnet-type solid electrolyte Li6.35Ga0.05La3Zr1.5Ta0.5O12Has an impedance of 10020 Ω and an ionic conductivity of 8.47×10-6S/cm, example 5 garnet-type solid electrolyte Li5.75Ga0.25La3Zr1.5Ta0.5O12Has an impedance of 28500. omega. and an ionic conductivity of 2.98X 10-6S/cm so that Li can be explained2CO3、La2O3、ZrO2、Ga2O3、Ta2O5The best effect is achieved at the ratio of 121:60:60:3:10, because the proper amount of doped Ga element can stabilize the cubic phase of the garnet-type solid electrolyte at room temperature, and if the doped Ga element ratio is too high, the content of Li in the garnet-type solid electrolyte is too low, which leads to the reduction of the ionic conductivity of the garnet-type solid electrolyte, and finally, the proper element ratio selected in example 3 is beneficial to obtain the garnet-type solid electrolyte with the optimal electrochemical performance.
Garnet-type solid electrolyte Li prepared by double doping modification of example 36.05Ga0.15La3Zr1.5Ta0.5O12And comparative example 1 undoped modified garnet-type solid electrolyte Li7La3Zr2O12Its structure and performance was tested by XRD, SEM and EIS.
Carrying out XRD analysis by using the sintered garnet type solid electrolyte; as shown in fig. 4, the results of investigating the type and content of the phase in the garnet-type solid electrolyte revealed that: undoped garnet structure electrolyte containing tetragonal phase and cubic phase, and double-doped garnet solid electrolyte with pure cubic structure is obtained;
observing the section of the sintered garnet solid electrolyte sheet by adopting SEM to obtain the growth condition of the garnet solid electrolyte crystal; as shown in fig. 5, the undoped density is low and the grain size is large, and the double-doped density is high and the grain size is small;
as shown in fig. 6, through the calculation of Zview fitting, the garnet type solid electrolyte Li prepared by double doping modification at 65 DEG C6.05Ga0.15La3Zr1.5Ta0.5O12Has an impedance of 72.164 omega and an ionic conductivity of 1.18X 10-3S/cm; comparative example 1Doping modified garnet type solid electrolyte Li7La3Zr2O12Has an impedance of 116495 omega and an ionic conductivity of 7.29X 10-7S/cm; the modified garnet-type solid electrolyte has higher ion conductivity because the undoped modified garnet-type solid electrolyte is a tetragonal phase, the Li ions of the garnet-type solid electrolyte are orderly arranged and have poorer conductivity, and the garnet-type solid electrolyte modified by double doping is a cubic phase, the Li ions of the garnet-type solid electrolyte are randomly arranged and have strong conductivity and higher ion conductivity.
As shown in FIG. 7, the garnet-type solid electrolyte Li was measured at a temperature ranging from 25 ℃ to 85 ℃6.05Ga0.15La3Zr1.5Ta0.5O12The EIS atlas obtains the ionic conductivity at different temperatures, and the garnet-type solid electrolyte prepared in the embodiment 3 of the invention has better conductivity within the range of 25-85 ℃.
The relationship between the ionic conductivity and the temperature of the garnet-type solid electrolyte can be characterized by the Arrhenius equation sigma (A/T) exp (-Ea/kT), and the garnet-type solid electrolyte Li can be found by using (ln sigma T) as the ordinate and (1000/T) as the abscissa6.05Ga0.15La3Zr1.5Ta0.5O12The ion conductivity and the temperature are in a linear relation; as shown in fig. 8, the fitted linear equation is y-3.725 x +10.051, and the activation energy Ea of ion transport can be calculated by using the slope of the straight line, and the activation energy Ea is 0.32 eV.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. A solid electrolyte for a lithium ion battery, characterized in that: the lithium titanate/lanthanum oxide/zirconium dioxide/gallium oxide/tantalum pentoxide composite material is prepared by mixing lithium carbonate, lanthanum oxide, zirconium dioxide, gallium oxide and tantalum pentoxide at a molar ratio of 115-127: 58-62: 1-5: 10.
2. The method of claim 1, wherein the method comprises the steps of: the method comprises the following steps:
s1, lanthanum oxide presintering: weighing lanthanum oxide powder for sintering, wherein the sintering condition is as follows: the heating rate is 2-5 ℃/min, the temperature is increased to 800-1000 ℃, and the heat preservation time is 8-12 h;
s2, first ball milling: mixing and stirring lanthanum oxide pre-sintered in the step S1 with lithium carbonate, zirconium dioxide, gallium oxide and tantalum pentoxide to obtain a powder raw material, adding zirconium dioxide balls, pouring into a ball milling tank, pouring an isopropanol solution until the powder raw material and the zirconium dioxide balls are submerged, and carrying out ball milling for 10-15 h at the ball milling speed of 150-300 rpm;
s3, primary drying: after the first ball milling is finished, putting the obtained slurry into a drying oven at 100-200 ℃ for drying for 20-30 h to obtain powder I;
s4, pre-sintering: taking out the powder I, pouring the powder I into a crucible, compacting, pre-sintering, wherein the sintering conditions are as follows: heating to 900-1000 ℃ at a heating rate of 1-4 ℃/min, preserving heat for 3-8 h, and cooling to obtain powder II;
s5, secondary ball milling: taking out the powder II of the S4, adding zirconium dioxide balls, pouring into a ball milling tank, pouring an isopropanol solution until the powder raw materials and the zirconium dioxide balls are submerged, and carrying out ball milling for 10-15 h at the ball milling speed of 150-300 rpm;
s6, drying for the second time: after the second ball milling is finished, putting the obtained slurry into a drying oven at 100-200 ℃ for drying for 20-30 h to obtain doped and modified garnet-type solid electrolyte powder;
s7, tabletting: adding a polyvinyl alcohol solution into the doped and modified garnet type solid electrolyte powder, stirring, drying for 3-8 min, taking out the dried powder, sieving by using a combined screen, collecting the powder, carrying out hot pressing at normal temperature, and respectively pressing into a wafer and a gasket;
s8, sintering: stacking a plurality of wafers into a platinum crucible, placing a gasket on the uppermost layer, respectively paving doped and modified garnet type solid electrolyte powder between the wafers and between the wafers, and performing four-stage sintering, wherein in the first stage, the temperature is raised to 80-120 ℃ at 20-30 ℃, the temperature raising rate is 2-4 ℃/min, the temperature is kept for 1-3 h, in the second stage, the temperature is raised to 400-500 ℃, the temperature raising rate is 2-4 ℃/min, the temperature is kept for 1-3 h, in the third stage, the temperature is raised to 1050-1150 ℃, the temperature raising rate is 1-3 ℃/min, the temperature is kept for 10-20 h, in the fourth stage, the temperature is lowered to 20-30 ℃, and the temperature lowering rate is 3-8 ℃/min; and after sintering, taking out the sheet and storing the sheet in a vacuum drying oven.
3. The method of claim 2, wherein the method comprises the steps of: the zirconium dioxide balls are divided into big balls and small balls, the diameter of the big balls is 8-12 mm, the diameter of the small balls is 3-6 mm, and the mass ratio of the powder raw materials to the big balls to the small balls is 1: 1-3: 3-5.
4. The method of claim 2, wherein the method comprises the steps of: the ball milling methods in S2 and S5 are that each ball milling is carried out for 1 hour, the time is suspended for 0.5 hour, the ball milling rotation direction of the ball mill is changed, and the ball milling is continued.
5. The method of claim 2 for preparing a solid electrolyte for a lithium ion battery, wherein: preparing a polyvinyl alcohol solution in the S7 tabletting: according to the mass ratio of 1: 8-15, weighing polyvinyl alcohol and deionized water, pouring the polyvinyl alcohol into the deionized water, heating the deionized water to 80-120 ℃, and stirring by using a magnetic stirrer until the polyvinyl alcohol is completely dissolved in the deionized water to obtain a polyvinyl alcohol solution.
6. The method of claim 2, wherein the method comprises the steps of: the sintering in the S8 is divided into four sections, wherein in the first section, the temperature is raised to 100 ℃ at 25 ℃, the heating rate is 3 ℃/min, and the heat is preserved for 2h, in the second section, the temperature is raised to 450 ℃ at 100 ℃, the heating rate is 3 ℃/min, the heat is preserved for 2h, in the third section, the temperature is raised to 1100 ℃ at 450 ℃, the heating rate is 1 ℃/min, the heat is preserved for 15h, and in the fourth section, the temperature is lowered to 25 ℃ at 1100 ℃, and the temperature lowering rate is 5 ℃/min.
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| CN115403381A (en) * | 2022-09-29 | 2022-11-29 | 华中科技大学 | Ceramic solid electrolyte, preparation method thereof and lithium ion battery |
| CN115763955A (en) * | 2022-11-30 | 2023-03-07 | 海南大学 | Solid electrolyte with lithium-philic surface and preparation method thereof |
| CN115724662A (en) * | 2022-12-01 | 2023-03-03 | 淄博火炬能源有限责任公司 | Oxide solid electrolyte and preparation process thereof |
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