CN112397776B - Ga and Al co-doped LLZO solid electrolyte, multi-element solid battery and preparation method thereof - Google Patents
Ga and Al co-doped LLZO solid electrolyte, multi-element solid battery and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M2300/0068—Solid electrolytes inorganic
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Abstract
The invention belongs to the technical field of all-solid-state batteries, and particularly relates to a Ga and Al co-doped LLZO solid electrolyte, a multi-element solid-state battery and a preparation method thereof. The preparation method effectively solves the core problems of the three solid batteries of the growth of lithium dendrites, low coulomb effect and interface side reaction by introducing the Ga and Al co-doped LLZO inorganic oxide solid electrolyte and the quantum carbon-based film/metal composite interface layer.
Description
Technical Field
The invention relates to a Ga and Al co-doped LLZO solid electrolyte, a multi-element solid cell and a preparation method thereof, belonging to the technical field of solid cells.
Background
The inorganic oxide solid electrolyte has the advantages of high thermal stability, chemical stability, good ion conductivity, large potential window, relatively high calcination density, no environmental pollution and controllable process conditions, and gradually becomes an important material of a new generation of all-solid power battery. The garnet type solid electrolyte (LLZO) is the electrolyte with the best comprehensive performance in oxide electrolytes, and the LLZO solid electrolyte not only has the conductivity as high as 10 < -4 > S/cm to 10 < -3 > S/cm, but also has the chemical stability to Li and the shear modulus of 56GPa to 60GPa, so that the LLZO solid electrolyte can be used as the core material of the next generation battery, namely an all-solid battery.
Because the LLZO electrolyte is in a tetragonal phase structure at room temperature, the structure causes lower ionic conductivity, the cubic phase LLZO structure needs to be obtained by element doping, and the element doping is an effective means for stabilizing the cubic phase and improving the density of a ceramic sample, particularly doping with Al, Y and Ga. These dopants not only can replace the corresponding elements in the LLZO lattice but also contribute to the formation of low melting point phases by the grain boundaries.
Unlike the electrolyte, the LLZO electrolyte has high strength and high brittleness, and is difficult to be in full contact with the positive and negative electrode materials, the interface impedance between the electrolyte and the electrode is huge due to the insufficient solid-solid contact, the impedance of a poor negative electrode/electrolyte interface is about 1K Ω · cm2 level, the impedance of a positive electrode/electrolyte interface which is not modified is often higher than 1M Ω · cm2, and the high interface impedance makes the solid battery incapable of operating at room temperature, so the interface problem is the first obstacle faced by the practical application of the LLZO to the solid battery.
In addition to the interface problem, another major problem of the LLZO electrolyte in battery application is the lithium dendrite growth problem, which is originally thought that the inorganic solid electrolyte has high strength and cannot be penetrated by lithium dendrites, so that the lithium dendrite problem does not exist, but research shows that lithium ions passing through an ion channel of the LLZO electrolyte reach a negative electrode unevenly, and a gap also exists between the solid electrolyte and the negative electrode interface, so that irregular deposition of the lithium ions is easily caused, and lithium dendrites are formed, once the lithium dendrites appear, which means that the lithium ions inside the battery are irreversibly reduced, and the lithium dendrites continuously adsorb free lithium ions to realize growth, and finally, the separator may be penetrated, so that the positive electrode and the negative electrode of the battery directly contact to cause short circuit.
The invention aims to solve the problems in the prior art, and the gallium and aluminum doped LLZO electrolyte is prepared by a two-step sintering method, and a quantum carbon-based film/metal interface layer is introduced into a positive electrode/electrolyte interface and a negative electrode/electrolyte interface, so that a high-quality Ga and Al co-doped LLZO solid electrolyte battery is finally prepared, and the battery shows excellent electrochemical performance and can prevent lithium dendrites.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a Ga and Al co-doped LLZO solid electrolyte, a multi-element solid battery and a preparation method thereof.
The technical problem of the invention is solved by the following technical scheme:
the Ga and Al co-doped LLZO solid electrolyte is characterized in that the structural expression is Li7-3x- 3yAlyGaxLa3Zr2O12Wherein x is more than 0 and less than or equal to 0.02, and y is more than 0 and less than or equal to 0.04.
The preparation method of the Ga and Al co-doped LLZO solid electrolyte is characterized in that the method adopts Ga and Al co-doping to prepare the cubic phase garnet type Lithium Lanthanum Zirconium Oxide (LLZO) solid electrolyte, and comprises the following steps:
s1: according to the formula Li7-3x-3yAlyGaxLa3Zr2O12Wherein x is more than 0 and less than or equal to 0.02, y is more than 0 and less than or equal to 0.04, and lithium hydroxide monohydrate (LiOH. H) is respectively weighed2O), lanthanum oxide (La)2O3) Zirconium dioxide (ZrO)2) Gallium trioxide (Ga)2O3) Aluminum trioxide (Al)2O3)。
S2: sintering the lanthanum sesquioxide, mixing the lanthanum sesquioxide with the lithium hydroxide monohydrate and the zirconium dioxide after sintering, and adding gallium sesquioxide and aluminum trioxide into the mixture according to a proportion;
s3: performing wet ball milling on the mixture;
s4: drying the raw materials subjected to ball milling and mixing;
s5: grinding and refining the dried raw materials, and pre-sintering to obtain a precursor material;
s6: tabletting the precursor material;
s7: calcining the pressed sheet to obtain Ga and Al co-doped Li7-3x-3yAlyGaxLa3Zr2O12An inorganic oxide solid electrolyte.
The preparation method of the Ga and Al co-doped LLZO solid electrolyte is characterized in that,
sintering the lanthanum sesquioxide in a muffle furnace at 900 ℃ for 12h in S2;
s5, grinding and refining the raw materials, and pre-sintering at 950 ℃ for 6h to obtain a precursor material;
the calcining temperature in S7 is 1000 ℃, 1050 ℃, 1100 ℃ or 1150 ℃, and the calcining time is 12 h.
The preparation method of the Ga and Al co-doped LLZO solid electrolyte is characterized in that the Ga and Al co-doped Li7-3x-3yAlyGaxLa3Zr2O12The inorganic oxide solid electrolyte is nanocrystal particles, the particle size is below 2000nm, and the particle size of the gallium trioxide and aluminum trioxide particles is below 400 nm.
The preparation method of the Ga and Al co-doped LLZO solid electrolyte is characterized in that the mass fractions of the used raw materials are 30-35 wt% of lithium hydroxide monohydrate, 45-55 wt% of lanthanum trioxide, 15-20 wt% of zirconium dioxide, more than 0 and less than or equal to 2 wt% of gallium trioxide, more than 0 and less than or equal to 4 wt% of aluminum trioxide, and the total mass is 100 wt%.
The preparation method of the Ga and Al co-doped LLZO solid electrolyte is characterized in that the purity of the lithium hydroxide monohydrate, the lanthanum sesquioxide, the zirconium dioxide, the gallium sesquioxide and the aluminum trioxide is more than 99 percent.
The multi-element solid-state battery is characterized by comprising the Ga and Al co-doped LLZO solid electrolyte as claimed in claim 1, and further comprising a positive pole piece and a multi-element negative pole piece.
The multi-element solid battery is characterized in that the positive pole piece consists of a positive active material and interface layers symmetrically sandwiched with two sides of the positive active material, wherein the positive active material layer is an organic biomass porous active material, and the interface layers are of a composite structure of a quantum carbon-based film and a metal coating; the negative pole piece consists of a negative pole active material layer and interface layers symmetrically sandwiched with two sides of the negative pole active material layer, wherein the negative pole active material layer is a gallium-doped lithium-nickel-manganese (Li-Ni-Mn-Ga) multi-element alloy material, and the interface layers are of a composite structure of a quantum carbon-based film and a metal coating.
The multi-element solid-state battery is characterized in that the preparation method of the organic biomass porous active material comprises the following steps: firstly, drying an organic biomass raw material, then carrying out ball milling on the dried raw material, then carrying out temperature programming carbonization on the ball-milled material under the protection of nitrogen atmosphere, and naturally cooling to room temperature to prepare the corresponding organic biomass porous active material positive active material layer.
The multi-element solid-state battery pole piece is characterized in that the organic biomass raw material is at least one of starch and arrowroot.
The multi-element solid-state battery is characterized in that,
the preparation method of the positive pole piece comprises the following steps:
a1: firstly, coating or sputtering a layer of metal protective coating on the quantum carbon-based film, wherein the metal is one of nickel, silver and tin;
a2: coating a positive active material layer according to claim 9 on the metal coating layer of a 1;
a3: repeating A1-A2 on another carbon-based film, and then performing hot-pressing compounding with the coating material obtained in A2 to form a quantum carbon-based film/metal protective layer/positive electrode material/metal protective layer/quantum carbon-based film multi-layer composite positive electrode piece;
the preparation method of the multielement negative pole piece comprises the following steps:
b1: firstly, coating or sputtering a layer of metal protective coating on the quantum carbon-based film, wherein the metal is one of nickel, silver and tin;
b2: coating the metal coating layer of B1 with a layer of the negative active material of claim 8;
b3: repeating B1-B2 on another carbon-based film, and then performing hot-press compounding with the coating material obtained in B2 to form the multi-layer composite multi-element negative pole piece of the quantum carbon-based film/the metal protective layer/the negative pole material/the metal protective layer/the quantum carbon-based film.
The multi-element solid-state battery is characterized in that the preparation method of the gallium-doped lithium nickel manganese multi-element alloy (Li-Ni-Mn-Ga) material comprises the following steps: at least 85% of metallic lithium by weight is placed in a molten alloy bath at the temperature of below-50 ℃ under the vacuum condition, and then the metallic lithium is heated to 200-800 ℃ to be molten; then adding 0.01-5% of nickel and 0.01-5% of manganese by weight into the molten bath, and stirring for 30 min; and then adding 0.01-2% of gallium into the molten bath, keeping stirring for 30 minutes to completely dissolve gallium particles and homogenizing the liquid mixture to form molten alloy, and then cooling to room temperature to obtain the corresponding gallium-doped lithium nickel manganese multi-element alloy (Li-Ni-Mn-Ga) material negative electrode active material layer.
The multi-element solid-state battery is characterized in that the gallium-doped lithium nickel manganese multi-element alloy (Li-Ni-Mn-Ga) material comprises at least 85% of metal lithium, 0.01-5% of metal nickel, 0.01-5% of metal manganese and 0.01-2% of metal gallium in parts by weight.
The preparation method of the multi-element solid-state battery is characterized in that the Ga and Al co-doped LLZO inorganic oxide solid-state electrolyte, the positive plate and the negative plate are sequentially laminated and assembled, and then the battery shell is used for sealing to obtain the multi-element solid-state battery pole piece.
Compared with the prior art, the invention has the advantages that:
(1) the invention can effectively solve the core problems of the solid-state batteries such as lithium dendrite growth, low coulomb effect and interface side reaction, and is beneficial to promoting the industrialization of the solid-state battery technology;
(2) according to the invention, the LLZO inorganic oxide solid electrolyte with higher sintering density is obtained by doping gallium and aluminum to the LLZO oxide solid electrolyte at the same time, the ionic conductivity of the electrolyte is improved, and the performance of the solid electrolyte is far better than that of the undoped LLZO oxide solid electrolyte.
(3) According to the invention, the interface treatment is respectively carried out on the positive and negative electrode layers, the possibility of side reactions between the solid electrolyte and the positive and negative electrodes is blocked by introducing the quantum carbon-based film/metal interface layer, the normal performance and the cyclability of the solid battery in the working process are ensured to the maximum extent, the formation of lithium dendrites can be effectively prevented, an SEI film passivation layer cannot be generated between the solid electrolyte and the positive and negative electrodes, the coulombic efficiency is improved, and the attenuation of discharge capacity is greatly slowed down.
(4) The invention respectively carries out coating treatment of the metal layer on the positive and negative electrode layers, and increases the contact surface between the positive and negative electrode active materials and the electrolyte interface, thereby improving the impedance performance of the solid-solid interface between the positive electrode and the electrolyte and improving the coulombic efficiency of the battery. In addition, the good conductivity of the metal coating can also realize the reduction of impedance, so as to improve the coulomb efficiency of the battery system.
By adopting the technical scheme, the multi-element solid-state battery pole piece based on the Ga and Al co-doped garnet-type LLZO solid electrolyte prepared by the invention has excellent performances of high ionic conductivity, good stability and the like, and can better solve the problem of lithium dendrite. The multielement solid-state battery pole piece prepared by the technical scheme of the invention can realize high energy density of 900Wh/L, charge and discharge cycles of more than 1000 times, coulombic efficiency of more than 95 percent, good safety performance and wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the synthesis process of Ga and Al co-doped LLZO oxide solid electrolyte
FIG. 2 is an SEM image of Ga and Al co-doped LLZO oxide solid electrolyte of the present invention
FIG. 3 is a BSE-SEM image of LLZO co-doped garnet-type LLZO solid electrolyte with different Ga and Al doping ratios (from left to right, x is 0.00, y is 0.40, x is 0.05, y is 0.30, x is 0.10, y is 0.20, x is 0.15, y is 0.15, x is 0.20, y is 0.00)
FIG. 4 is a graph of conductivity of LLZO co-doped garnet-type LLZO solid electrolyte at different Ga and Al doping ratios according to the present invention
Detailed Description
The invention will be further described with reference to the accompanying drawings and preferred embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
It should be noted that the terms of orientation such as left, right, up, down, top and bottom in the present embodiment are only relative concepts to each other or are referred to the normal use state of the product, and should not be considered as limiting.
Example 1 (preparation of Ga, Al co-doped LLZO solid electrolyte)
According to the formula Li7-3x-3yAlxGayLa3Zr2O12(wherein x is 0.15 and y is 0.15) in a molar ratio, lithium hydroxide monohydrate (LiOH · H) was weighed out separately2O), lanthanum oxide (La)2O3) Zirconium dioxide (ZrO)2) Gallium trioxide (Ga)2O3) Aluminum trioxide (Al)2O3) Adding La2O3Sintering the raw materials in a muffle furnace at 900 ℃ for 12 hours, mixing the raw materials with lithium hydroxide monohydrate, zirconium dioxide, gallium trioxide and aluminum trioxide after sintering, putting the mixture into a ball milling tank, and performing wet ball milling on the raw materials for 10 hours by taking isopropanol as a dispersion medium (ball milling balls and the ball milling tank are made of zirconium oxide materials) to ensure that the raw materials are uniformly mixed; drying the ball-milled and mixed raw materials in a vacuum oven at 80 ℃ for 12 hours; grinding and refining the dried and uniformly mixed raw materials, and pre-sintering for 6 hours at 950 ℃ to obtain a precursor material; weighing a certain mass of the precursor material obtained by pre-sintering, and tabletting by a manual powder tabletting machine (the pressure is 18MPa, and the diameter of the tablet is 13 mm); and (3) carrying out second-step calcination on the pressed sheet, covering the pressed sheet with precursor material powder in the calcination process to reduce the volatilization of lithium in the calcination process, wherein the sintering temperature in the sintering process is 1000 ℃, and the sintering time is 12 hours, so that the prepared sheet is ceramic. Ga. Al co-doped Li7-3x-3yAlyGaxLa3Zr2O12The inorganic oxide solid electrolyte is nanocrystal particles, the particle size is below 2000nm, and the particle size of the gallium trioxide and aluminum trioxide particles is below 400 nm.
Example 2 (preparation of Positive electrode sheet)
Drying starch for 24 hours at 100 ℃ in an air atmosphere, then ball-milling the dried starch at the rotating speed of 300r/min for 6 hours, finally putting the ball-milled starch into a quartz tube furnace, keeping the temperature of the ball-milled starch at 200 ℃ for 1 hour at the heating rate of 10 ℃/min under the protection of nitrogen atmosphere, keeping the temperature at 500 ℃ for 1 hour, and naturally cooling the mixture to room temperature to obtain the anode active material. Coating the positive active material slurry on a quantum carbon-based film coated with a layer of nano silver metal protection to obtain two coating materials, and then carrying out hot-pressing compounding on the two coating materials to form the multilayer composite positive pole piece of the quantum carbon-based film/the metal protective layer/the positive material/the metal protective layer/the quantum carbon-based film.
Example 3 preparation of a Multi-element negative electrode sheet
Under the vacuum condition at the temperature lower than-50 ℃, 90 percent of metallic lithium by weight is put into a molten alloy bath, and then the metallic lithium is melted by heating the metallic lithium to the temperature of 300 ℃; then adding 5% of nickel and 3% of manganese by weight into the molten bath, and stirring for 30 min; then 2% gallium was added to the molten bath and stirring was maintained for 30 minutes to completely dissolve the gallium particles and homogenize the liquid mixture to form a molten alloy, which was then cooled to room temperature to produce a gallium-doped lithium nickel manganese multi-active material.
Coating the cathode active material slurry on a quantum carbon-based film coated with a layer of nano silver metal protection to obtain two coating materials, and then carrying out hot-pressing compounding on the two coating materials to form the multi-layer composite multi-element cathode pole piece of the quantum carbon-based film/the metal protective layer/the cathode material/the metal protective layer/the quantum carbon-based film.
Example 4 preparation of a Multi-element solid State Battery Pole piece
The multi-layer composite multi-element negative electrode piece of the quantum carbon-based film/the metal protection layer/the negative electrode material/the metal protection layer/the quantum carbon-based film of example 3, the Ga and Al co-doped LLZO solid electrolyte obtained in example 1, and the multi-layer composite positive electrode piece of the quantum carbon-based film/the metal protection layer/the positive electrode material/the metal protection layer/the quantum carbon-based film obtained in example 2 are sequentially stacked and assembled, and are sealed by a battery shell to obtain the multi-element solid battery electrode piece.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.
Claims (6)
1. The multi-element solid battery is characterized by comprising Ga and Al co-doped LLZO solid electrolyte, a positive pole piece and a multi-element negative pole piece; the structural expression of the Ga and Al co-doped LLZO solid electrolyte is Li7-3x-3yAlyGaxLa3Zr2O12Wherein x is 0.05, y is 0.30 or x is 0.10, y is 0.20 or x is 0.15 and y is 0.15; the positive pole piece consists of a positive active material and interface layers symmetrically sandwiched with the two sides of the positive active material, wherein the positive active material layer is an organic biomass porous active material, and the interface layers are of a composite structure of a quantum carbon-based film and a metal coating; the negative pole piece consists of a negative active material layer and interface layers symmetrically sandwiched with two surfaces of the negative active material layer, wherein the negative active material layer is a gallium-doped Li-Ni-Mn-Ga material of a lithium-nickel-manganese multi-element alloy, and the interface layers are of a composite structure of a quantum carbon-based film and a metal coating.
2. The multi-element solid-state battery according to claim 1, wherein the organic biomass porous active material is prepared by: firstly, drying an organic biomass raw material, then carrying out ball milling on the dried raw material, then carrying out temperature programming carbonization on the ball-milled material under the protection of nitrogen atmosphere, and naturally cooling to room temperature to prepare the corresponding organic biomass porous active material positive active material layer.
3. The multi-element solid-state battery pole piece of claim 2, wherein the organic biomass material is at least one of starch and arrowroot.
4. The multi-element solid-state battery according to claim 1,
the preparation method of the positive pole piece comprises the following steps:
a1: firstly, coating or sputtering a layer of metal protective coating on the quantum carbon-based film, wherein the metal is one of nickel, silver and tin;
a2: coating a layer of the positive active material layer on the metal coating layer A1;
a3: repeating A1-A2 on another carbon-based film, and then performing hot-pressing compounding with the coating material obtained in A2 to form a quantum carbon-based film/metal protective layer/positive electrode material/metal protective layer/quantum carbon-based film multi-layer composite positive electrode piece;
the preparation method of the multielement negative pole piece comprises the following steps:
b1: firstly, coating or sputtering a layer of metal protective coating on the quantum carbon-based film, wherein the metal is one of nickel, silver and tin;
b2: coating a layer of the negative active material layer on the metal coating layer B1;
b3: repeating B1-B2 on another carbon-based film, and then performing hot-press compounding with the coating material obtained in B2 to form the multi-layer composite multi-element negative pole piece of the quantum carbon-based film/the metal protective layer/the negative pole material/the metal protective layer/the quantum carbon-based film.
5. The multi-element solid-state battery according to claim 1, wherein the gallium-doped Li-Ni-Mn-Ga material is prepared by: at least 85% of metallic lithium by weight is placed in a molten alloy bath at the temperature of below-50 ℃ under the vacuum condition, and then the metallic lithium is heated to 200-800 ℃ to be molten; then adding 0.01-5% of nickel and 0.01-5% of manganese by weight into the molten bath, and stirring for 30 min; and then adding 0.01-2% of gallium into the molten bath, keeping stirring for 30 minutes to completely dissolve gallium particles and homogenizing the liquid mixture to form molten alloy, and then cooling to room temperature to obtain the corresponding gallium-doped lithium-nickel-manganese multi-element alloy Li-Ni-Mn-Ga material cathode active material layer.
6. The multi-element solid state battery according to claim 5, wherein the gallium-doped lithium nickel manganese multi-element alloy (Li-Ni-Mn-Ga) material comprises, in parts by weight, at least 85% of metallic lithium, 0.01 to 5% of metallic nickel, 0.01 to 5% of metallic manganese, and 0.01 to 2% of metallic gallium.
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| CN113363562B (en) * | 2021-05-19 | 2022-09-30 | 万向一二三股份公司 | Preparation method of low-resistivity garnet-type modified LLZO solid electrolyte |
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| CN114552129B (en) * | 2021-07-13 | 2023-10-03 | 万向一二三股份公司 | Double-sided differential lithium battery diaphragm and lithium battery comprising same |
| CN113461050B (en) * | 2021-07-20 | 2024-01-23 | 中国科学院上海硅酸盐研究所 | Porous LLZO ceramic powder inhibitor for thermal battery electrolyte and preparation method thereof |
| CN113903985B (en) * | 2021-09-17 | 2024-02-23 | 海南大学 | Solid electrolyte buffer layer and preparation method thereof |
| CN114349045B (en) * | 2021-12-28 | 2022-09-27 | 广东马车动力科技有限公司 | Preparation method of high-yield pure-phase lithium lanthanum zirconium oxide solid electrolyte material |
| CN114349507A (en) * | 2021-12-31 | 2022-04-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for improving sintering relative density of lithium lanthanum zirconium oxygen ceramic wafer |
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