CN115642292A - Zero-strain all-solid-state lithium-aluminum battery - Google Patents
Zero-strain all-solid-state lithium-aluminum battery Download PDFInfo
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Abstract
The invention belongs to the technical field of batteries, and particularly relates to a zero-strain all-solid-state lithium-aluminum battery. The zero-strain all-solid-state lithium-aluminum battery comprises a lithium-based positive electrode, an aluminum-based negative electrode and all-solid-state electrolyte, wherein the aluminum-based negative electrode comprises a multi-layer microporous aluminum-based material. According to the invention, zero-strain materials are used as the anode and the cathode, and after the all-solid-state battery is assembled with a sulfide electrolyte, the all-solid-state battery gradually forms a whole in the circulation process, so that the generation of pores and stress concentration are avoided, the material transmission in the electrode is ensured, the circulation is more stable, and the problems of poor interface contact and rapid capacity attenuation of the all-solid-state battery are solved.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a zero-strain all-solid-state lithium-aluminum battery.
Background
Lithium batteries have been widely used in mobile electronic devices, electric vehicles, smart grids, etc., however, organic liquid electrolytes in commercial lithium ion batteries are flammable due to low flash points of carbonates, and especially under high voltage conditions, this often causes potential safety hazards in practical applications. Therefore, the all-solid-state battery using the solid electrolyte attracts a great deal of attention because the all-solid-state battery has no liquid inside, has no fluidity, and can stably operate under conditions of high temperature, high voltage, and large current without short circuit and battery failure. In addition, because the traditional liquid lithium ion battery needs to use a diaphragm occupying part of the volume and mass of the battery, and the solid electrolyte can be compatible with a high-capacity anode and cathode material, the all-solid-state battery has higher mass energy density, lighter weight and higher volume energy density.
However, all-solid batteries still have some disadvantages such as low ionic conductivity of the solid electrolyte, inherent rigidity and brittleness of the solid electrolyte, high interfacial resistance between the solid electrolyte and the electrode, and the like. What is not negligible is that the volume of the electrode changes to different degrees due to the continuous intercalation and deintercalation of lithium ions during the charge and discharge cycles of the battery, i.e., the electrode changes in volume, i.e., expands or contracts. When the electrode volume shrinks, the contact between the electrode and the electrolyte becomes not tight any more, and even micro cracks occur, so that the battery is easy to break and further fails.
Disclosure of Invention
The invention aims to provide a zero-strain all-solid-state lithium-aluminum battery aiming at the defects of all-solid-state batteries in the prior art.
A zero-strain all-solid-state lithium-aluminum battery comprises a lithium-based positive electrode, an aluminum-based negative electrode and an all-solid-state electrolyte, wherein the aluminum-based negative electrode comprises a multi-layer microporous aluminum-based material.
The aluminum-based negative electrode adopted by the zero-strain all-solid-state lithium-aluminum battery comprises a multi-layer microporous aluminum-based material, a continuum without stress concentration is formed by introducing multi-layer micropores into the aluminum-based material, and the multi-layer microporous aluminum-based material serving as the negative electrode can not only increase the active area of the electrode, but also prevent the negative electrode from generating longitudinal strain in the charging and discharging processes.
Preferably, the multilevel microporous aluminum-based material comprises one or two of nanopores and micropores.
Preferably, the diameter range of the nanometer hole is 1 to 500nm, and the diameter range of the micrometer hole is 1 to 2000 μm.
Preferably, the multi-level microporous aluminum-based material further comprises anisotropic pores formed by various textures such as plate texture and silk texture.
Preferably, the multilevel microporous aluminum-based material comprises orderly arranged vertical nano-pores and vertical micro-pores, staggered micro-pores and nano-pores, irregularly-shaped pores with various textures and the like.
Preferably, the porosity of the multilevel microporous aluminum-based material is 15 to 80 percent.
Preferably, the porosity of the multilevel microporous aluminum-based material is 15 to 80 percent, and the pore size distribution is as follows: the volume of the nanopores is at least 10% of the total pore volume.
Preferably, the multilevel microporous aluminum-based material is an aluminum-based material and is prepared by a pore-forming method.
Preferably, the pore-forming method includes, but is not limited to, one or more of a hard template method, a freeze-drying method, a microwave etching method, a laser drilling method, a hydrothermal method, a solvothermal method, a muffle furnace etching method, and a 3D printing method.
Preferably, the aluminum-based material includes, but is not limited to, one or more of aluminum, aluminum-magnesium alloy, aluminum-silicon alloy, aluminum-carbon alloy, aluminum-manganese alloy, aluminum-copper alloy, and aluminum-nickel alloy.
Preferably, the lithium-based positive electrode includes one or more selected from the group consisting of: the high-entropy anode material, the composite material of the ternary anode material and the lithium cobaltate, and the composite material of the high-entropy anode material, the ternary anode material and the lithium cobaltate. The lithium-based positive electrode can be a high-entropy positive electrode material, can also be a composite material of a ternary positive electrode material and lithium cobaltate, and can further be a composite material of the high-entropy positive electrode material, the ternary positive electrode material and the lithium cobaltate. The lithium-based positive electrode adopted by the invention is a zero-strain material, the high-entropy positive electrode material almost has no volume strain in the battery charging and discharging process, and the volume of the lithium cobaltate positive electrode in the composite material of the ternary positive electrode material and the lithium cobaltate material is shrunk in the discharging process and is mutually offset with the volume expansion of the ternary positive electrode, so that the volume strain is avoided.
Preferably, the high-entropy cathode material has a general formula shown in formula I:
LiAO 2 the compound of the formula I is shown in the specification,
wherein A is selected from five elements or more of Ni, co, mn, al, mg, mo, nb, V, ti, zr and Zn.
Preferably, the ternary cathode material has a general formula shown in formula II:
LiNi x Co y Mn 1-x-y O 2 in the formula II, the compound is shown in the specification,
wherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
Preferably, the mass ratio of the ternary cathode material to the lithium cobaltate is 1:99 to 99:1, more preferably 7:3 to 9:1.
preferably, the lithium-based positive electrode is a composite material of a high-entropy positive electrode material, a ternary positive electrode material and lithium cobaltate. When the lithium-based positive electrode is a composite material of a high-entropy positive electrode material, a ternary positive electrode material and lithium cobaltate, the assembled all-solid-state lithium-aluminum battery has almost no volume strain in the charge and discharge processes, and has more excellent cycling stability.
Preferably, in the composite material of the high-entropy cathode material, the ternary cathode material and the lithium cobaltate, the mass percentage of the high-entropy cathode material is 10-50%, the total mass percentage of the ternary cathode material and the lithium cobaltate is 50-90%, and the mass ratio of the ternary cathode material to the lithium cobaltate is 1:99 to 99:1.
preferably, the aluminum-based negative electrode has a thickness of 1 to 500 μm, more preferably 5 to 50 μm.
Preferably, the all-solid-state electrolyte has a general formula shown in formula III:
xLi a B·yC c D d ·zP 2 S 5 in the formula (III), the compound is shown in the formula,
wherein x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, z is more than or equal to 0 and less than 100, a is 1 or 2, C is 1 or 2, D is 1, 2 or 5, B is one or more of S, cl, br and I, C is one or more of Li, si, ge, P, sn and Sb, and D is one or more of Cl, br, I, O, S and Se.
According to the invention, the lithium-based anode and the aluminum-based cathode are zero-strain materials, and are assembled with the sulfide electrolyte to form the all-solid-state battery, so that the all-solid-state battery gradually forms a whole in the circulating process, the generation of pores and stress concentration are avoided, the material transmission in the electrode is ensured, the circulation is more stable, and the problems of poor interface contact and rapid capacity attenuation of the all-solid-state battery are solved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The multi-level microporous aluminum-based material is used as the negative electrode, so that the active area of the electrode can be increased, and the negative electrode can be greatly inhibited from generating strain in the charging and discharging processes;
(2) The high-entropy anode material or the composite material of the ternary anode material and the lithium cobaltate or the composite material of the high-entropy anode material, the ternary anode material and the lithium cobaltate is used as the anode, the high-entropy material almost has no volume strain in the charging and discharging process, and the volume of the lithium cobaltate anode in the composite material shrinks in the discharging process and is mutually offset with the volume expansion of the ternary anode, so that the volume strain is avoided;
(3) According to the invention, zero-strain materials are used as the anode and the cathode, and after the all-solid-state battery is assembled with a sulfide electrolyte, the all-solid-state battery gradually forms a whole in the circulation process, so that the generation of pores and stress concentration are avoided, the material transmission in the electrode is ensured, the circulation is more stable, and the problems of poor interface contact and rapid capacity attenuation of the all-solid-state battery are solved;
(4) When the composite material of the high-entropy anode material, the ternary anode material and the lithium cobaltate is used as the anode, the constructed all-solid-state lithium-aluminum battery has more excellent cycle stability.
Drawings
FIG. 1 is a graph of capacity versus voltage at 0.1C cycle rate for a cell of comparative example 1;
fig. 2 is a graph of capacity-coulombic efficiency at 0.1C cycle rate for the cell of comparative example 1;
FIG. 3 is a graph of capacity versus voltage for the cell of comparative example 2 at 0.1C cycle rate;
fig. 4 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of comparative example 2;
fig. 5 is a graph of capacity versus voltage for the cell of example 1 at 0.1C cycle rate;
fig. 6 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 1;
fig. 7 is a graph of capacity versus voltage for the cell of example 2 at 0.1C cycle rate;
fig. 8 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 2;
fig. 9 is a graph of capacity versus voltage for the cell of example 3 at 0.1C cycle rate;
fig. 10 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 3;
fig. 11 is a graph of capacity versus voltage for the cell of example 4 at 0.1C cycle rate;
fig. 12 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 4;
fig. 13 is a graph of capacity versus voltage for the cell of example 5 at 0.1C cycle rate;
fig. 14 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 5;
fig. 15 is a graph of capacity versus voltage for the cell of example 6 at 0.1C cycle rate;
fig. 16 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 6;
fig. 17 is a graph of capacity versus voltage for the cell of example 7 at 0.1C cycle rate;
fig. 18 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 7;
fig. 19 is a graph of capacity versus voltage for the cell of example 8 at 0.1C cycle rate;
fig. 20 is a graph of capacity versus coulombic efficiency at 0.1C cycling rate for the cell of example 8;
fig. 21 is a graph of capacity versus voltage for the cell of example 9 at 0.1C cycle rate;
fig. 22 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 9;
fig. 23 is a graph of capacity versus voltage for the cell of example 10 at 0.1C cycle rate;
fig. 24 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 10;
FIG. 25 is a graph of capacity versus voltage for the cell of example 11 at 0.1C cycle rate;
fig. 26 is a graph of capacity versus coulombic efficiency at 0.1C cycle rate for the cell of example 11.
Detailed Description
The technical solutions of the present invention are further described below by way of specific embodiments and drawings, it should be understood that the specific embodiments described herein are only for the purpose of facilitating understanding of the present invention, and are not intended to be specific limitations of the present invention. And the drawings used herein are for the purpose of illustrating the disclosure better and are not intended to limit the scope of the invention. The experimental methods used in the following examples are all conventional methods unless otherwise specified; materials used in the following examples, and the like, unless otherwise specified, raw materials in the examples of the present application were all purchased from commercial sources; the instruments used in the following examples, unless otherwise specified, were set to the manufacturer's recommended parameters.
Comparative example 1
Preparation of an aluminum foil having a negative electrode without any treatment, electrolyte being sulfide electrolyte L according to the following procedure 6 PS 5 Cl and LiNi as ternary positive electrode 0.8 Co 0.1 Mn 0.1 O 2 The all-solid-state battery of (2):
(1) Sequentially ultrasonically cleaning pure aluminum foil without any treatment and with the thickness of about 20 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Mixing the aluminum foil and a ternary positive electrode LiNi 0.8 Co 0.1 Mn 0.1 O 2 With a sulfide electrolyte L 6 PS 5 The Cl assembles into an all solid state battery.
The assembly method of the all-solid-state battery specifically comprises the following steps: cutting the obtained aluminum-based negative electrode into small wafers with the diameter of 10 mm; weighing 150mg of solid sulfide electrolyte, and compacting the solid sulfide electrolyte; 3mg of the positive electrode material was weighed and uniformly spread on the solid electrolyte. And (3) assembling an all-solid-state battery in the glove box filled with argon, wherein the all-solid-state battery sequentially comprises a steel sheet, a positive electrode, sulfide electrolyte, an aluminum-based negative electrode and the steel sheet from top to bottom, and compacting by using a press to obtain the all-solid-state battery.
And (3) carrying out charge and discharge tests on the all-solid-state battery under the following test conditions: and (3) setting the temperature to be 30 ℃, setting the standing time to be 2h, setting the charge-discharge cut-off voltage to be 2.7-3.9V and setting the circulation multiplying power to be 0.1C for circulation until the coulombic efficiency is subjected to unstable fluctuation, and ending the program.
The results of the all-solid battery of comparative example 1 are shown in fig. 1 and 2, and the specific charge capacity is 172.0mAh g -1 The specific discharge capacity is 163.6mAh g -1 The capacity retention rate is 52.5% after 500 cycles.
Comparative example 2
Preparation of an aluminum foil having a negative electrode without any treatment, electrolyte being sulfide electrolyte L according to the following procedure 6 PS 5 Cl, and an all-solid-state battery with a positive electrode made of lithium cobaltate material:
(1) Sequentially ultrasonically cleaning pure aluminum foil without any treatment and with the thickness of about 20 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Mixing the aluminum foil, lithium cobaltate material and sulfide electrolyte L 6 PS 5 The Cl assembles into an all solid state battery.
The all-solid-state battery assembly method is the same as the above, and the all-solid-state battery charge and discharge test steps are the same as the above.
The results of the all-solid battery of comparative example 2 are shown in fig. 3 and 4, and the specific charge capacity is 138.3mAh g -1 The specific discharge capacity is 123.0mAh g -1 The capacity retention rate is 65.6% after 500 cycles.
Example 1
The porous aluminum foil with zero strain as the negative electrode and the sulfide electrolyte Li as the electrolyte are prepared according to the following steps 6 PS 5 Cl and LiNi with ternary positive electrode 0.8 Co 0.1 Mn 0.1 O 2 The all-solid-state battery of (a):
(1) Sequentially ultrasonically cleaning pure aluminum foil without any treatment and with the thickness of about 20 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Performing laser double-sided punching on the aluminum foil by using a laser punching method, wherein the punching depth is 10 mu m, and the laser spot diameter is 50 mu m;
(3) Preparing 200mL of 25mM nickel nitrate solution, and soaking the aluminum foil obtained in the step (2) in the nickel nitrate solution for 30 minutes to fully soak the aluminum foil;
(4) Taking out the aluminum foil obtained in the step (3), placing the aluminum foil into a cleaned porcelain ark, placing the porcelain ark into a muffle furnace, preserving the heat at 200 ℃ for 3 minutes, taking out the porcelain ark after the heat preservation is finished, respectively and sequentially carrying out ultrasonic cleaning in deionized water and absolute ethyl alcohol, and then drying to obtain a zero-strain porous aluminum foil;
(5) Wherein the pore structure of the zero strain porous aluminum foil comprises: (a) The structure comprises (a) orderly arranged vertical micron-sized pores, (b) staggered micro-sized pores and nano-sized pores, wherein the diameter of the micro-sized pores is 50 mu m, the diameter of the nano-sized pores is 50 to 200nm, the porosity is 70%, and the volume of the nano-sized pores accounts for 20% of the total pore volume;
(6) Mixing the zero-strain porous aluminum foil and the ternary positive electrode LiNi 0.8 Co 0.1 Mn 0.1 O 2 With sulfide electrolyte Li 6 PS 5 The Cl assembles into an all solid state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid battery of example 1 are shown in fig. 5 and 6, and the specific charge capacity is 179.7mAh g -1 The specific discharge capacity is 177.4mAh g -1 The capacity retention rate at 500 cycles was 73.6%.
Example 2
An aluminum foil having a negative electrode without any treatment was prepared according to the following procedure, the electrolyte being sulfide electrolyte Li 7 P 3 S 11 The positive electrode is a ternary positive electrode LiNi 0.8 Co 0.1 Mn 0.1 O 2 The all-solid-state battery of (a):
(1) Sequentially ultrasonically cleaning pure aluminum foil without any treatment and with the thickness of about 20 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Mixing the aluminum foil and a ternary positive electrode LiNi 0.8 Co 0.1 Mn 0.1 O 2 With sulfide electrolyte Li 7 P 3 S 11 And assembling to form the all-solid-state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid battery of example 2 are shown in fig. 7 and 8, and the specific charge capacity is 170.1mAh g -1 The specific discharge capacity is 168.1mAh g -1 The capacity retention rate after 500 cycles was 69.4%.
Example 3
An aluminum foil having a negative electrode without any treatment, an electrolyte being a sulfide electrolyte Li, was prepared according to the following procedure 6 PS 5 Cl, high-entropy positive electrode with zero strain as positive electrode, ternary positive electrode and lithium cobaltate composite material LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.0 1 Ti 0.016 O 2 / LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The all-solid-state battery of (a):
(1) Sequentially ultrasonically cleaning pure aluminum foil without any treatment and with the thickness of about 20 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Weighing LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 50mg、LiNi 0.8 Co 0.1 Mn 0.1 O 2 80mg and 20mg of lithium cobaltate positive electrode are fully ground in a glove box under the protection of argon atmosphere to obtain a zero-strain mixed positive electrode;
(3) Mixing the aluminum foil, the zero-strain mixed anode and the sulfide electrolyte Li 6 PS 5 The Cl assembles into an all solid state battery.
The all-solid-state battery assembly method is the same as the above, and the all-solid-state battery charge and discharge test steps are the same as the above.
The results of the all-solid battery of example 3 are shown in fig. 9 and 10, and the specific charge capacity is 176.3mAh g -1 To putThe specific capacity is 174.8 mAh g -1 The capacity retention rate is 75.2% after 500 cycles.
Example 4
Preparing a porous aluminum foil with zero strain as a negative electrode and sulfide electrolyte Li as an electrolyte according to the following steps 6 PS 5 Cl, high-entropy positive electrode with zero strain as positive electrode, ternary positive electrode and lithium cobaltate composite material LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 /LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The all-solid-state battery of (2):
(1) Sequentially ultrasonically cleaning pure aluminum foil without any treatment and with the thickness of about 20 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Performing laser double-sided punching on the aluminum foil by using a laser punching method, wherein the punching depth is 10 mu m, and the laser spot diameter is 50 mu m;
(3) Preparing 200mL of 25mM nickel nitrate solution, and soaking the aluminum foil obtained in the step (2) in the nickel nitrate solution for 30 minutes to fully soak the aluminum foil;
(4) Taking out the aluminum foil obtained in the step (3), placing the aluminum foil into a cleaned porcelain ark, placing the porcelain ark into a muffle furnace, preserving the heat at 200 ℃ for 3 minutes, taking out the porcelain ark after the heat preservation is finished, respectively and sequentially carrying out ultrasonic cleaning in deionized water and absolute ethyl alcohol, and then drying to obtain a zero-strain porous aluminum foil;
(5) Wherein the pore structure of the porous aluminum foil comprises: (a) The method comprises the following steps of (a) orderly arranged vertical micron-sized holes, (b) staggered micro-sized holes and nano-holes, wherein the diameter of each micro-hole is 50 micrometers, the diameter of each nano-hole is 50 to 200nm, the porosity is 70%, and the volume of each nano-hole accounts for 20% of the total pore volume;
(6) Weighing 50mg of a high-entropy positive electrode, 80mg of a ternary positive electrode and 20mg of a lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain mixed positive electrode;
(7) Mixing the zero-strain porous aluminum foil, the zero-strain mixed anode and the sulfide electrolyte Li 6 PS 5 The Cl assembles into an all solid state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid battery of example 4 are shown in fig. 11 and 12, and the specific charge capacity is 184.8 mAh g -1 Discharge specific capacity of 175.8 mAh g -1 The capacity retention rate is 89.2% after 500 cycles.
Example 5
The method comprises the following steps of preparing a porous aluminum-silicon alloy as a negative electrode, and preparing a sulfide electrolyte Li as an electrolyte 4 PS 4 I. The positive electrode is a zero-strain high-entropy positive electrode and a ternary positive electrode and lithium cobaltate composite material LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 / LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The all-solid-state battery of (a):
(1) Respectively ultrasonically cleaning aluminum-silicon alloy (the aluminum content is 89wt percent and the silicon content is 11wt percent) which is not treated and has the thickness of about 10 mu m in deionized water and absolute ethyl alcohol in sequence, and then drying;
(2) Using a hard template method, carrying out close packing on spherical silicon oxide particles to form a planar structure as a template, introducing an aluminum-silicon alloy into the template, then placing the template in a 12.5mM ferric nitrate solution, adjusting the pH value to 10, removing the template, and leaving micron-sized holes;
(3) Sequentially ultrasonically cleaning in deionized water and absolute ethyl alcohol respectively, and then drying to obtain a zero-strain porous aluminum-silicon alloy;
(4) Wherein the porous aluminum-silicon alloy has a pore structure comprising: (a) Ordered vertical micron-sized pores, (b) irregularly shaped pores consisting of plate textures, wherein the micron pores have a diameter of 150 μm and a porosity of 55%;
(5) Weighing 50mg of a high-entropy positive electrode, 75mg of a ternary positive electrode and 25mg of a lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain mixed positive electrode;
(6) The electrolyte is sulfide electrolyte Li 4 PS 4 I；
(7) And assembling the zero-strain porous aluminum-silicon alloy, the zero-strain mixed anode and the sulfide electrolyte into an all-solid-state battery.
The all-solid-state battery assembly method is the same as the above, and the all-solid-state battery charge and discharge test steps are the same as the above.
The results of the all-solid battery of example 5 are shown in fig. 13 and 14, and the specific charge capacity is 186.6mAh g -1 The specific discharge capacity is 178.7 mAh g -1 The capacity retention rate of 500 cycles is 92.9%.
Example 6
The method comprises the following steps of preparing a zero-strain porous aluminum-magnesium alloy as a negative electrode, and preparing a sulfide electrolyte Li as an electrolyte 7 P 2 S 8 I. The positive electrode is a zero-strain high-entropy positive electrode and a ternary positive electrode and lithium cobaltate composite material LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.0 2 Nb 0.01 Ti 0.016 O 2 /LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The all-solid-state battery of (a):
(1) Respectively ultrasonically cleaning an aluminum-magnesium alloy (the aluminum content is 70wt percent and the magnesium content is 30wt percent) which has no treatment and has the thickness of about 30 mu m in deionized water and absolute ethyl alcohol in sequence, and then drying;
(2) Performing laser double-sided punching on the aluminum-magnesium alloy by using a laser punching method, wherein the punching depth is 10 mu m, and the laser spot diameter is 500 mu m;
(3) Preparing 200mL of 25mM nickel nitrate solution, and soaking the aluminum-magnesium alloy obtained in the step (2) in ferric nitrate solution for 30 minutes to fully soak the aluminum-magnesium alloy;
(4) Taking out the aluminum-magnesium alloy obtained in the step (3), placing the aluminum-magnesium alloy into a cleaned porcelain ark, then placing the porcelain ark into a microwave oven with the power of 800W and the microwave for 30s, taking out the porcelain ark after the microwave oven is finished, respectively and sequentially carrying out ultrasonic cleaning in deionized water and absolute ethyl alcohol, and then drying to obtain the zero-strain porous aluminum-magnesium alloy;
(5) Wherein the porous aluminum magnesium alloy has a pore structure comprising: the composite material comprises (a) orderly arranged vertical micropores and nanopores, (b) staggered micropores and nanopores, and (c) special-shaped pores consisting of fiber textures and plate textures, wherein the diameter of the micropores is 500 micrometers, the diameter of the nanopores is 80-150nm, the porosity is 40%, and the volume of the nanopores accounts for 55% of the total pore volume;
(6) Weighing 50mg of a high-entropy positive electrode, 85mg of a ternary positive electrode and 15mg of a lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain mixed positive electrode;
(7) The electrolyte is sulfide electrolyte Li 7 P 2 S 8 I；
(8) And assembling the zero-strain porous aluminum-magnesium alloy, the zero-strain mixed anode and the sulfide electrolyte into an all-solid-state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid battery of example 6 are shown in fig. 15 and 16, and the specific charge capacity is 189.6mAh g -1 The specific discharge capacity is 189.1mAh g -1 The capacity retention rate is 93.7% after 500 cycles.
Example 7
The method comprises the following steps of preparing a porous aluminum-copper alloy with zero strain as a negative electrode and sulfide electrolyte Li as an electrolyte 10 GeP 2 S 12 And the positive electrode is a zero-strain high-entropy positive electrode LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 The all-solid-state battery of (2):
(1) Sequentially ultrasonically cleaning aluminum-copper alloy (the aluminum content is 97wt% and the copper content is 3 wt%) with the thickness of about 35 mu m without any treatment in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Preparing 50mL of 25mM nickel nitrate solution, transferring the nickel nitrate solution to a substrate of a reaction kettle, and placing the aluminum-copper alloy obtained in the step (1) at the bottom of the substrate;
(3) Placing the reaction kettle in an oven, keeping the temperature at 200 ℃ for 6h, taking out after the reaction kettle is finished, respectively and sequentially carrying out ultrasonic cleaning in deionized water and absolute ethyl alcohol, and then drying to obtain a zero-strain porous aluminum-copper alloy;
(4) Wherein the porous aluminum copper alloy has a pore structure comprising: (a) The composite material comprises (a) staggered nano-scale holes, (b) special-shaped holes formed by fiber textures and plate textures, wherein the diameter of each nano-scale hole is 50-250nm, and the porosity is 20%;
(5) The zero-strain porous aluminum-copper alloy, the zero-strain high-entropy anode and sulfide electrolyte Li are mixed 10 GeP 2 S 12 And assembling the battery into an all-solid-state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid battery of example 7 are shown in fig. 17 and 18, and the specific charge capacity is 193.2mAh g -1 The specific discharge capacity is 192.9mAh g -1 The capacity retention rate is 88.6% after 500 cycles.
Example 8
The method comprises the following steps of preparing the porous aluminum-manganese alloy with zero strain as the negative electrode and sulfide as the electrolyte Li 5.4 PS 4.4 Cl 1.6 The anode is a zero-strain high-entropy anode and a ternary anode and lithium cobaltate composite material LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 /LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The all-solid-state battery of (2):
(1) Sequentially ultrasonically cleaning an aluminum-manganese alloy (the aluminum content is 98.5wt percent, and the manganese content is 1.5wt percent) without any treatment and with the thickness of about 45 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Performing laser double-sided punching on the aluminum-manganese alloy by using a laser punching method, wherein the punching depth is 10 mu m, and the laser spot diameter is 1800 mu m;
(3) Adding 3g of nickel nitrate powder into 50mL of ethanol, stirring until the nickel nitrate powder is completely dissolved, transferring the mixture into a substrate of a reaction kettle, and placing the aluminum-manganese alloy obtained in the step (1) at the bottom of the substrate;
(3) Placing the reaction kettle in an oven, preserving heat for 12 hours at 150 ℃, taking out after the reaction kettle is finished, respectively and sequentially carrying out ultrasonic cleaning in deionized water and absolute ethyl alcohol, and then drying to obtain a zero-strain porous aluminum-manganese alloy;
(4) Wherein the porous aluminum manganese alloy has a pore structure comprising: (a) The composite material comprises (a) orderly arranged vertical micropores and nanopores, (b) special-shaped pores consisting of fiber textures, wherein the diameter of the micropores is 1800 mu m, the diameter of the nanopores is 100 to 300nm, the porosity is 60 percent, and the volume of the nanopores accounts for 35 percent of the total pore volume;
(5) Weighing 50mg of a high-entropy positive electrode, 90mg of a ternary positive electrode and 10mg of a lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain mixed positive electrode;
(6) The zero-strain porous aluminum-manganese alloy, the zero-strain mixed anode and the sulfide electrolyte Li are mixed 5.4 PS 4.4 Cl 1.6 And assembling the battery into an all-solid-state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid-state battery of example 8 are shown in fig. 19 and 20, and the specific charge capacity is 202.2mAh g -1 The specific discharge capacity is 192.5mAh g -1 The capacity retention rate after 500 cycles is 91.2%.
Example 9
The preparation method comprises the following steps of preparing a zero-strain porous aluminum-carbon alloy as a negative electrode and preparing a sulfide electrolyte Li as an electrolyte 10 GeP 2 S 12 The anode is a ternary anode and a lithium cobaltate composite anode LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The all-solid-state battery of (a):
(1) Sequentially ultrasonically cleaning an aluminum-carbon alloy (the aluminum content is 97wt% and the carbon content is 3 wt%) which is not processed and has the thickness of about 200 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Performing laser double-sided drilling on the aluminum-carbon alloy by using a laser drilling method, wherein the drilling depth is 10 mu m, and the laser spot diameter is 800 mu m;
(3) Preparing 200mL of 25mM nickel nitrate solution, and soaking the aluminum-carbon alloy obtained in the step (2) in the nickel nitrate solution for 30 minutes to fully soak the aluminum-carbon alloy;
(4) Taking out the aluminum-carbon alloy obtained in the step (3), placing the aluminum-carbon alloy in a cleaned porcelain ark, placing the porcelain ark in a muffle furnace, keeping the temperature at 200 ℃ for 3 minutes, taking out the aluminum-carbon alloy after the heat preservation, respectively carrying out ultrasonic cleaning in deionized water and absolute ethyl alcohol in sequence, and then drying to obtain a zero-strain porous aluminum-carbon alloy;
(5) Wherein the porous aluminum carbon alloy has a pore structure comprising: (a) Staggered micro-pores and nano-pores, (b) special-shaped pores composed of fiber textures, wherein the diameter of the micro-pores is 800 μm, the diameter of the nano-pores is 80 to 150nm, the porosity is 40%, and the volume of the nano-pores accounts for 45% of the total pore volume;
(6) Weighing 40mg of ternary positive electrode and 60mg of lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain composite positive electrode;
(7) The zero-strain porous aluminum-carbon alloy, the zero-strain composite anode and the sulfide electrolyte Li are mixed 10 GeP 2 S 12 And assembling to form the all-solid-state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid battery of example 9 are shown in fig. 21 and 22, and the specific charge capacity is 193.3mAh g -1 Discharge specific capacity of 191.7 mAh g -1 The capacity retention rate after 500 cycles is 90.0%.
Example 10
The method comprises the following steps of preparing a porous aluminum-nickel alloy with zero strain as a negative electrode and sulfide electrolyte Li as an electrolyte 5.5 PS 4.5 Cl 1.5 The anode is a zero-strain high-entropy anode and a ternary anode and lithium cobaltate composite material LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 /LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The all-solid-state battery of (2):
(1) Sequentially ultrasonically cleaning aluminum-nickel alloy (the content of aluminum is 52wt% and the content of nickel is 48 wt%) which has the thickness of 35 mu m and is not subjected to any treatment in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Performing physical pore-forming on the aluminum-nickel alloy by using a freeze-drying method, dispersing a pore-forming agent polystyrene sphere in gelatin, placing the aluminum-nickel alloy in the gelatin, and standing for 24 hours;
(3) Taking out the aluminum-nickel alloy, fully freezing the aluminum-nickel alloy to ensure that the solvent is sublimated from the aluminum-nickel alloy, leaving pores on the aluminum-nickel alloy, and then cleaning and drying the aluminum-nickel alloy by using deionized water;
(4) Preparing 200mL of 25mM nickel nitrate solution, and soaking the aluminum-nickel alloy obtained in the step (3) in the nickel nitrate solution for 30 minutes to fully soak the aluminum-nickel alloy;
(5) Taking out the aluminum-nickel alloy obtained in the step (4), placing the aluminum-nickel alloy in a cleaned porcelain ark, placing the porcelain ark in a microwave oven with the power of 800W and the microwave for 30s, taking out the aluminum-nickel alloy after the microwave oven is finished, respectively and sequentially carrying out ultrasonic cleaning in deionized water and absolute ethyl alcohol, and then drying to obtain a zero-strain porous aluminum-nickel alloy;
(6) Wherein the porous aluminum nickel alloy has a pore structure comprising: (a) The composite material comprises (a) staggered micro-pores and nano-pores, (b) a special-shaped pore composed of a fiber texture and a plate texture, wherein the diameter of the micro-pores is 180 micrometers, the diameter of the nano-pores is 80-150nm, the porosity is 60%, and the volume of the nano-pores accounts for 60% of the total pore volume;
(7) Weighing 50mg of a high-entropy positive electrode, 80mg of a ternary positive electrode and 20mg of a lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain mixed positive electrode;
(8) The zero-strain porous aluminum-nickel alloy, the zero-strain mixed anode and the sulfide electrolyte Li are added 5.5 PS 4.5 Cl 1.5 And assembling the battery into an all-solid-state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid battery of example 10 are shown in fig. 23 and 24, and the specific charge capacity is 192.9mAh g -1 The specific discharge capacity is 190.4 mAh g -1 The capacity retention rate is 92.4% after 500 cycles.
Example 11
The porous aluminum foil with zero strain as the negative electrode and the sulfide electrolyte Li as the electrolyte are prepared according to the following steps 3 PS 4 The anode is a ternary anode and a lithium cobaltate composite anode LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The all-solid-state battery of (a):
(1) Sequentially ultrasonically cleaning aluminum foil without any treatment and with the thickness of about 400 mu m in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Using a hard template method, carrying out close packing on spherical silicon oxide particles to form a planar structure as a template, introducing an aluminum-silicon alloy into the template, then placing the template in a 12.5mM ferric nitrate solution, adjusting the pH value to 10, removing the template, and leaving micron-sized holes;
(3) Adding 3g of nickel nitrate powder into 50mL of ethanol, stirring until the nickel nitrate powder is completely dissolved, transferring the nickel nitrate powder into a substrate of a reaction kettle, and placing the aluminum foil obtained in the step (2) at the bottom of the substrate;
(4) Placing the reaction kettle in an oven, preserving heat for 12h at 150 ℃, taking out after the reaction kettle is finished, respectively carrying out ultrasonic cleaning in deionized water and absolute ethyl alcohol in sequence, and then drying to obtain a zero-strain porous aluminum foil;
(5) Wherein the pore structure of the porous aluminum foil comprises: the composite material comprises micropores and nanopores which are arranged in a staggered mode, wherein the micropores are 1200 microns, the nanopores are 350-450nm, the porosity is 35%, and the volume of the nanopores accounts for 75% of the total pore volume;
(6) Weighing 20mg of ternary positive electrode and 80mg of lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain composite positive electrode;
(7) The zero-strain porous aluminum-silicon alloy, the zero-strain mixed anode and the sulfide electrolyte Li 3 PS 4 And assembling the battery into an all-solid-state battery.
The assembly method of the all-solid-state battery is the same as the above, and the charging and discharging test steps of the all-solid-state battery are the same as the above.
The results of the all-solid battery of example 11 are shown in fig. 25 and 26, and the specific charge capacity is 185.1mAh g -1 The specific discharge capacity is 183.5mAh g -1 The capacity retention rate after 500 cycles is 87.5%.
Example 12
Example 12 differs from example 4 in that the positive electrode of example 12 is a zero-strain high-entropy positive electrode LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 Otherwise, the same as in example 4.
Preparing a zero-strain porous aluminum foil and a zero-strain high-entropy positive electrode LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.01 6 O 2 With sulfide electrolyte Li 6 PS 5 The Cl assembles into an all solid state battery.
The specific charge capacity of the all-solid-state battery of example 12 was 182.6mAh g -1 Discharge specific capacity of 174.9mAh g -1 The capacity retention rate after 500 cycles is 85.6%.
Example 13
Example 13 differs from example 4 in that the positive electrode is a mixture LiNi of a ternary positive electrode and lithium cobaltate 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 The rest was the same as in example 4.
Weighing 80mg of ternary positive electrode and 20mg of lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain mixed positive electrode; a zero-strain porous aluminum foil, the zero-strain mixed anode and sulfide electrolyte Li 6 PS 5 The Cl assembles into an all solid state battery.
The specific charge capacity of the all-solid-state battery of example 13 was 183.2mAh g -1 The specific discharge capacity is 175.3mAh g -1 The capacity retention rate is 88.1% after 500 cycles.
Example 14
Example 14 differs from example 9 in that the positive electrode is a zero strain high entropy positive electrode LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 The rest was the same as in example 9.
Preparing zero-strain porous aluminum-carbon alloy and zero-strain high-entropy anode LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 With sulfide electrolyte Li 10 GeP 2 S 12 And assembling the battery into an all-solid-state battery.
The specific charge capacity of the all-solid battery of example 14 was 193.0mAh g -1 Discharge specific capacity of 191.2mAh g -1 The capacity retention rate is 88.4% after 500 cycles.
Example 15
Example 15 differs from example 9 in that the positive electrode was a zero strain high entropy positive electrode and a ternary positive electrode and lithium cobaltate composite material LiNi 0.776 Co 0.102 Mn 0.056 Mg 0.02 Mo 0.02 Nb 0.01 Ti 0.016 O 2 /LiNi 0.8 Co 0.1 Mn 0.1 O 2 /LiCoO 2 Otherwise, the same as in example 9.
Weighing 50mg of a high-entropy positive electrode, 40mg of a ternary positive electrode and 60mg of a lithium cobaltate positive electrode, and fully grinding in a glove box under the protection of argon atmosphere to obtain a zero-strain composite positive electrode; the zero-strain porous aluminum-carbon alloy, the zero-strain composite anode and the sulfide electrolyte Li are added 10 GeP 2 S 12 And assembling the battery into an all-solid-state battery.
The specific charge capacity of the all-solid-state battery of example 15 was 194.5mAh g -1 The specific discharge capacity is 192.5mAh g -1 The capacity retention rate is 91.2% after 500 cycles.
According to the embodiment and the comparative example, the multi-layer microporous aluminum-based material is used as the negative electrode, the high-entropy positive electrode material or the composite material of the ternary positive electrode material and lithium cobaltate or the composite material of the high-entropy positive electrode material, the ternary positive electrode material and the lithium cobaltate is used as the positive electrode, and the constructed all-solid-state lithium-aluminum battery has the advantages of no volume strain, more stable cycle and excellent capacity retention rate. When a composite material of a high-entropy positive electrode material, a ternary positive electrode material and lithium cobaltate is used as a positive electrode, the constructed all-solid-state lithium-aluminum battery has more excellent cycling stability under the same other conditions.
The aspects, embodiments, features of the present invention should be considered illustrative in all respects and not restrictive, the scope of the invention being defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
In the preparation method of the present invention, the order of the steps is not limited to the listed order, and for those skilled in the art, the order of the steps is not changed without creative efforts, and the invention is also within the protection scope of the present invention. Further, two or more steps or actions may be performed simultaneously.
Finally, it should be noted that the specific examples described herein are merely illustrative of the invention and do not limit the embodiments of the invention. Those skilled in the art may now make numerous modifications of, supplement, or substitute for the specific embodiments described, all of which are not necessary or desirable to describe herein. While the invention has been described with respect to specific embodiments, it will be appreciated that various changes and modifications can be made without departing from the spirit and scope of the invention, as defined by the appended claims.
Claims (10)
1. The zero-strain all-solid-state lithium-aluminum battery is characterized by comprising a lithium-based positive electrode, an aluminum-based negative electrode and an all-solid-state electrolyte, wherein the aluminum-based negative electrode comprises a multi-layer microporous aluminum-based material.
2. The zero-strain all-solid-state lithium-aluminum battery according to claim 1, wherein the multi-level microporous aluminum-based material comprises one or both of nanopores and micropores;
the diameter range of the nano-pores is 1 to 500nm, and the diameter range of the micro-pores is 1 to 2000 μm.
3. The zero-strain all-solid-state lithium-aluminum battery according to claim 1 or 2, wherein the multi-level microporous aluminum-based material is prepared by pore-forming method from aluminum-based material.
4. The zero-strain all-solid-state lithium-aluminum battery according to claim 3, wherein the pore-forming method comprises one or more of a hard template method, a freeze-drying method, a microwave etching method, a laser drilling method, a hydrothermal method, a solvothermal method, a muffle furnace etching method and a 3D printing method;
and/or the aluminum-based material comprises one or more of aluminum, aluminum-magnesium alloy, aluminum-silicon alloy, aluminum-carbon alloy, aluminum-manganese alloy, aluminum-copper alloy and aluminum-nickel alloy.
5. The zero-strain all-solid-state lithium aluminum battery according to claim 1, wherein the lithium-based positive electrode comprises one or more materials selected from the group consisting of: the high-entropy anode material, the composite material of the ternary anode material and the lithium cobaltate, and the composite material of the high-entropy anode material, the ternary anode material and the lithium cobaltate.
6. The zero-strain all-solid-state lithium-aluminum battery according to claim 5, wherein the high-entropy cathode material has a general formula shown in formula I:
LiAO 2 the compound of the formula I is shown in the specification,
wherein A is selected from five elements and more than five elements of Ni, co, mn, al, mg, mo, nb, V, ti, zr and Zn.
7. The zero-strain all-solid-state lithium-aluminum battery according to claim 5, wherein the ternary cathode material has a general formula shown in formula II:
LiNi x Co y Mn 1-x-y O 2 in the formula II, the compound is shown in the specification,
wherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
8. The zero-strain all-solid-state lithium-aluminum battery according to claim 5, wherein the mass ratio of the ternary cathode material to the lithium cobaltate is 1:99 to 99:1.
9. the zero-strain all-solid-state lithium-aluminum battery according to claim 1 or 5, wherein the lithium-based positive electrode is a composite material of a high-entropy positive electrode material, a ternary positive electrode material and lithium cobaltate.
10. The zero-strain all-solid-state lithium-aluminum battery according to claim 9, wherein in the composite material of the high-entropy cathode material, the ternary cathode material and the lithium cobaltate, the mass percentage of the high-entropy cathode material is 10 to 50%, and the total mass percentage of the ternary cathode material and the lithium cobaltate is 50 to 90%.
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