CN109921097B - Preparation method of all-solid-state battery and all-solid-state battery obtained by preparation method - Google Patents
Preparation method of all-solid-state battery and all-solid-state battery obtained by preparation method Download PDFInfo
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Abstract
The invention relates to a preparation method of an all-solid-state battery, which comprises the following steps: providing an all-solid-state electrolyte layer and a conversion reaction material composed of a sulfide, a fluoride, or an oxide of a metal; applying at least one conversion reaction material on at least one outer surface of the all-solid-state electrolyte layer to enable the conversion reaction material to be compounded with the all-solid-state electrolyte layer to form at least one coating layer, wherein the thickness of the coating layer is 0.1-2 mu m; a lithium negative electrode is applied to the cladding layer to react with the cladding layer to form a solid electrolyte interfacial film. The invention also provides an all-solid-state battery obtained by the preparation method. The preparation method of the all-solid-state battery is simple in process, can realize large-scale production, and is beneficial to industrial application of the all-solid-state battery. The obtained all-solid-state battery can prevent short circuit of the battery due to reduced interface resistance and inhibited dendrite formation, and improves the safety performance of the battery.
Description
Technical Field
The present invention relates to a solid-state battery, and more particularly, to a method of manufacturing an all-solid-state battery and an all-solid-state battery obtained thereby.
Background
An all-solid-state lithium battery is a device that is an energy storage device that is relatively liquid-state lithium battery, and that does not contain liquid in its structure, all of which exist in solid form. Specifically, it is composed of a positive electrode material, a negative electrode material and a solid electrolyte, while a liquid lithium battery is composed of a positive electrode material, a negative electrode material, an electrolyte and a separator.
In solid-state ionization, a solid-state electrolyte is an ionic conductor that has high ionic conductivity while blocking electron transport. Therefore, all-solid batteries using solid electrolytes generally have superior safety performance and higher energy density, and are therefore ideal batteries for electric vehicles.
The properties of the solid electrolyte material largely determine the power density, cycling stability, safety, high and low temperature performance, and service life of the battery. Common solid electrolytes can be classified into polymer electrolytes and inorganic electrolytes.
Polymer solid electrolyte
Taking polyethylene oxide (PEO) as an example, the polymer solid electrolyte has a stronger ability to dissociate lithium salt than other polymer matrixes and is stable to lithium, and currently, research focus in the field is mainly on PEO and derivatives thereof.
Inorganic solid electrolyte
In inorganic solid electrolyte, Li in garnet structure7La3Zr2O12As a representative, it has an ionic conductivity as high as 1mS/cm and good electrochemical/chemical stability, and is another research focus at present.
In a word, the inorganic solid electrolyte has the advantages of single ion conduction and high stability, is used in the all-solid-state lithium ion battery, has the advantages of high thermal stability, difficult combustion and explosion, environmental friendliness, high cycle stability, strong impact resistance and the like, is expected to be applied to novel lithium ion batteries such as lithium sulfur batteries, lithium air batteries and the like, and is the main direction of future electrolyte development.
At present, the most major problems in the application of inorganic solid electrolytes are:
first, since inorganic solid electrolytes tend to be hard ceramic materials and have poor interfacial wettability with lithium metal, a plating/cladding process is required to improve contact between the solid electrolyte and the lithium metal negative electrode.
Second, studies have shown that even solid electrolytes with higher mechanical strength produce lithium dendrites and tend to be more rapid than in a liquid electrolyte environment. The growth mechanism of a specific lithium dendrite in a solid electrolyte is not yet determined, but the mainstream view at present is that the lithium dendrite grows rapidly because the solid electrolyte is relatively stable with lithium metal, so that the lithium metal deposited in the grain boundaries and defects is hardly consumed, which further causes the tip electric field effect to accelerate the growth of the lithium dendrite along the grain boundaries.
Disclosure of Invention
In order to solve the problems of poor interfacial wettability and easy generation of dendrites in the prior art, the present invention aims to provide a method for manufacturing an all-solid battery and an all-solid battery obtained thereby.
The invention provides a preparation method of an all-solid-state battery, which comprises the following steps: s1, providing an all-solid-state electrolyte layer and a conversion reaction material composed of sulfide, fluoride or oxide of metal; s2, applying at least one conversion reaction material on at least one outer surface of the all-solid-state electrolyte layer to enable the conversion reaction material to be compounded with the all-solid-state electrolyte layer to form at least one coating layer, wherein the thickness of the coating layer is 0.1-2 mu m; s3, applying the lithium negative electrode on the coating layer to react with the coating layer to form a Solid Electrolyte Interface (SEI) film.
In particular, the conversion reaction material has the characteristic of conversion reaction with the lithium negative electrode, can dynamically react with the lithium negative electrode to form an SEI film, improves the physical contact between the lithium negative electrode and the all-solid-state electrolyte, reduces the interface resistance, and simultaneously inhibits the generation of metal dendrites.
Preferably, the all-solid electrolyte layer is formed of at least one material selected from the group consisting of Lithium Lanthanum Zirconium Oxide (LLZO), lithium phosphorus oxynitride (LIPON), Lithium Lanthanum Titanium Oxide (LLTO), lithium ion-rich anti-perovskite (LiRAP), and lithium germanium phosphorus sulfide (thio-LISICON). In practice, the all-solid-state electrolyte layer may be doped with at least one of the group consisting of tantalum, calcium, niobium, tungsten, aluminum, germanium elements to form the same type of fast ion conductor.
Preferably, the thickness of the all-solid electrolyte layer is 0.01mm to 1 mm. More preferably, the thickness of the all-solid electrolyte layer is 0.2mm to 0.8 mm.
Preferably, the conversion reaction material is at least one selected from the group consisting of molybdenum sulfide, copper fluoride, iron fluoride, copper sulfide, tin oxide, manganese oxide, iron oxide, and nickel oxide.
Preferably, the thickness of the coating layer is 0.2 μm to 2 μm.
Preferably, the conversion reaction material is compounded with the all-solid-state electrolyte by a casting or rolling process to form a clad layer. It should be understood that the conversion reaction material may also be compounded with the all-solid-state electrolyte by other simple processes.
The invention also provides an all-solid-state battery obtained by the preparation method.
Preferably, the coating layer reacts with the lithium negative electrode to produce Li-containing2S、Li2An interfacial film of at least one of the group consisting of O and LiF. In order to solve the problem of contact between a solid electrolyte and a negative electrode material in an all-solid-state battery, in the prior art, a plating layer is generally generated by alloying reaction of metal elementary substances such as Al, Au, Ge and the like and a lithium negative electrode. The interface film formed by the invention not only can improve the contact problem of the solid electrolyte and the negative electrode material, but also has lower electronic conductivity compared with the existing plating layer, and can prevent lithium dendrite from directly growing from the grain boundary and the defect of the solid electrolyte.
The preparation method of the all-solid-state battery is simple in process, can realize large-scale production, and is beneficial to industrial application of the all-solid-state battery. The obtained all-solid-state battery can prevent short circuit of the battery due to reduced interface resistance and inhibited dendrite formation, and improves the safety performance of the battery.
Drawings
Fig. 1 is a schematic view of the preparation of an all-solid battery according to example 1 of the invention;
fig. 2 is a schematic view of the preparation of an all-solid battery according to example 2 of the invention;
fig. 3 is a graph showing a cycle curve of a solid electrolyte of an all-solid battery of comparative example 1 according to the present invention;
fig. 4 is a graph showing the cycle curve of the solid electrolyte of the all-solid battery according to example 1 of the invention;
fig. 5 is a polarization graph of a solid electrolyte of an all-solid battery of comparative example 1 according to the present invention;
fig. 6 is a polarization graph of a solid electrolyte of an all-solid battery according to example 1 of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
Providing an all-solid-state electrolyte layer 1a, in particular, Li doped with Ta7La3Zr2O12The raw materials are mixed according to the stoichiometric ratio, and in order to make up for the loss of lithium in the high-temperature process, the using amount of the lithium-containing compound is excessive by 10 weight percent; is arranged at ZrO2Adding 30ml of isopropanol into a ball milling tank, and mixing for 15 hours by a planetary ball mill at the rotating speed of 900 r/min; drying the mixed raw material powder, and then calcining the dried raw material powder at 1150 ℃ for 10 hours; and ball-milling the obtained raw materials again to ensure that the calcined powder reaches a certain fineness, and then carrying out hot pressing on the powder for 1 hour at 1100 ℃ and 50Mpa by using a hot press to obtain the required LLZO solid electrolyte sheet with the thickness of about 0.8 mm.
A coating layer 1b is formed on the all-solid electrolyte 1a, specifically, conversion reaction material powder MoS is applied on the outer surface of the LLZO solid electrolyte sheet2Mo is rolled into a stainless steel cylinder (which has strong mechanical strength) by a roll forming methodS2The powder was spin-coated on the LLZO electrolyte sheet to form a coating layer 1b on the upper surface of the all-solid electrolyte 1a, as shown in fig. 1. Wherein the thickness of the coating layer can be simply controlled by repeating the spin coating times, and after one surface is coated, the MoS is coated in the same step2The powder is coated on the other side. In the present embodiment, the thickness of the clad layer 1b is about 1 μm.
And applying a metal negative electrode on the coating layer to react with the coating layer at 100 ℃, specifically, transferring the coated LLZO electrolyte sheet into a glove box, wherein the thickness of the LLZO electrolyte sheet is 0.8mm, and assembling the LLZO electrolyte sheet with two lithium sheets with the thickness of about 1.5mm in a Swagelok structure to form a lithium symmetrical all-solid-state battery.
Example 2
An all-solid electrolyte layer 2a of 0.8mm thickness was provided, copper fluoride as a conversion reaction material was applied on the outer surface of the LLTO solid electrolyte sheet, and this conversion reaction material slurry was caused to form a clad layer 2b of 2 μm thickness on the upper surface of the all-solid electrolyte layer 1b by a doctor blade of a casting method, as shown in FIG. 2. Finally, a lithium negative electrode was applied to the coating layer to react with the coating layer according to the same procedure as in example 1, and assembled with two lithium sheets having a thickness of about 1.5mm in a Swagelok structure to form a lithium symmetric all-solid battery.
Example 3
An all-solid electrolyte layer of 0.2mm thickness was provided, and nickel oxide, which is a conversion reaction material, was applied to the outer surface side of the LLZO solid electrolyte sheet to form a coating layer of 0.2 μm thickness. And finally, applying the lithium negative electrode on the coating layer to react with the coating layer to form the all-solid-state lithium battery.
It should be understood that although only the preparation of the negative electrode of the all-solid lithium battery is mentioned in the above embodiments, in practice, the all-solid lithium battery may include any known positive electrode, for example, applying a mass ratio of 4: 1: 5 LiFePO4Conductive carbon, solid electrolyte to form an associated positive electrode.
Comparative example 1
It differs from example 1 only in that no coating layer is provided.
The electrochemical performance of the all-solid batteries provided in example 1 and comparative document 1 was tested.
(1) And (3) interface resistance and cycle performance testing: heating the all-solid-state battery in a glove box (water, oxygen value less than 1ppm) to 100 deg.C for 1 hr, and heating the all-solid-state battery at 100 deg.C to 0.2mA/cm2And carrying out cyclic charge and discharge at the current density, wherein the charge and discharge time of each section is 30 min.
(2) Lithium dendrite inhibition ability test: at 100 ℃, the all-solid-state battery is heated at 0.2mA/cm2The charging and discharging cycle test is carried out under the condition of starting to gradually increase the current density, and the step length of each progressive process is 0.1mA/cm2Until short-circuiting or polarization occurs.
The results show that the all-solid battery of example 1 can ensure that the battery has a lower interfacial resistance and excellent lithium dendrite suppression capability during charging and discharging by introducing a material capable of undergoing a conversion reaction through the coating layer and finally forming an SEI film, thereby improving the capacity density and safety performance of the all-solid battery.
In comparative example 1, where the hard garnet-type oxide solid electrolyte was in poor physical contact with lithium metal, as shown in fig. 3, the cycling voltage of the assembled lithium symmetrical battery was large and stabilized at about 30mV, and it can be concluded that lithium metal had a large interfacial resistance when directly contacted with the solid electrolyte.
In example 1, MoS2The coating layer and the lithium metal have conversion reaction, the physical/chemical contact between the solid electrolyte and the lithium metal is improved, as shown in figure 4, the cycle voltage of the assembled lithium symmetrical battery is obviously reduced to about 8mV, and the interface resistance is greatly reduced.
In comparative example 1, in which the solid electrolyte is less stable to lithium and lithium dendrite is easily formed to cause short-circuiting of the battery, as shown in FIG. 5, the assembled lithium symmetrical battery was at 0.7mA/cm2A voltage dip phenomenon occurs due to rapid growth of lithium dendrites along grain boundaries and defects of the solid electrolyte, resulting in short-circuiting of the solid electrolyte.
In example 1, MoS2The interface layer blocks electronsThe junction to the surface defects of the solid electrolyte reduces the tip field effect, as shown in fig. 6, thereby inhibiting rapid growth of lithium dendrites along grain boundaries. At the same time, MoS2Can generate conversion reaction with lithium metal dynamically, and when the local current density is too large, Li is generated2The S/Mo layer inhibits the growth of lithium dendrites, so that the transmission of interface ions is more uniform.
The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.
Claims (6)
1. A preparation method of an all-solid-state battery is characterized by comprising the following steps:
s1, providing an all-solid-state electrolyte layer and a conversion reaction material composed of sulfide, fluoride or oxide of metal, wherein the conversion reaction material is at least one selected from the group consisting of molybdenum sulfide, copper fluoride and nickel oxide;
s2, applying at least one conversion reaction material on at least one outer surface of the all-solid-state electrolyte layer to enable the conversion reaction material to be compounded with the all-solid-state electrolyte layer to form at least one coating layer, wherein the thickness of the coating layer is 0.1-2 mu m;
s3, applying the lithium negative electrode on the clad layer to react with the clad layer to form a solid electrolyte interface film.
2. The production method according to claim 1, wherein the all-solid-state electrolyte layer is formed from at least one material selected from the group consisting of lithium lanthanum zirconium oxide, lithium phosphorus oxynitride, lithium lanthanum titanium oxide, lithium-rich ion anti-perovskite, and lithium germanium phosphorus sulfide.
3. The production method according to claim 1, wherein the thickness of the all-solid electrolyte layer is 0.01mm to 1 mm.
4. The method of claim 1, wherein the conversion reaction material is compounded with the all-solid-state electrolyte to form a clad layer by a casting or rolling process.
5. An all-solid battery obtained by the production method according to any one of claims 1 to 4.
6. The all-solid battery according to claim 5, wherein the clad layer reacts with the lithium negative electrode to produce Li-containing lithium2S、Li2An interfacial film of at least one of the group consisting of O and LiF.
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| CN111106380B (en) * | 2019-12-30 | 2020-12-15 | 华南师范大学 | Preparation method of solid electrolyte with surface coating and solid electrolyte battery |
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| CN113659198B (en) * | 2021-07-29 | 2023-06-23 | 青岛中科赛锂达新能源技术合伙企业(有限合伙) | All-solid-state electrolyte and application thereof in lithium sodium battery |
| CN114284475B (en) * | 2021-12-20 | 2024-01-30 | 中南大学 | Preparation method of three-dimensional structured composite lithium metal anode and product thereof |
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