CN116845393A - Solid lithium ion battery - Google Patents

Solid lithium ion battery Download PDF

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Publication number
CN116845393A
CN116845393A CN202311117548.XA CN202311117548A CN116845393A CN 116845393 A CN116845393 A CN 116845393A CN 202311117548 A CN202311117548 A CN 202311117548A CN 116845393 A CN116845393 A CN 116845393A
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halide
layer
lithium
electrolyte layer
solid electrolyte
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冯玉川
李峥
何泓材
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Suzhou Qingtao New Energy S&T Co Ltd
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Suzhou Qingtao New Energy S&T Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture

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  • Materials Engineering (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application provides a solid lithium ion battery, which comprises a positive electrode, a negative electrode and a composite solid electrolyte layer arranged between the positive electrode and the negative electrode, wherein a lithium metal supplementing layer is arranged between the composite solid electrolyte layer and the negative electrode, the negative electrode comprises a negative electrode active substance, and the negative electrode active substance comprises a silicon-based active material; the composite solid electrolyte layer comprises a sulfide solid electrolyte layer and a halide solid electrolyte layer which are adjacently arranged; the sulfide solid electrolyte layer is adjacent to the lithium metal supplementing layer, and the halide solid electrolyte layer is adjacent to the positive electrode; the sulfide solid electrolyte in the sulfide solid electrolyte layer is Li 6 PS 5 Cl; the halide solid electrolyte in the halide solid electrolyte layer is Li 2 ZrCl 6 Or Li (lithium) 2+e1‑f1 Zr 1‑e1‑f1 A e1 B f1 X 6 Or Li (lithium) 2+e2+2f2 Zr 1‑e2‑f2 M e2 N f2 Y 6 . The application improves the electrochemical performance of the battery.

Description

Solid lithium ion battery
Technical Field
The application relates to the technical field of batteries, in particular to a solid-state lithium ion battery.
Background
In the formation process of the lithium ion battery, a large amount of active lithium is consumed by the formation of the negative electrode SEI film, and particularly, in the case of adding part of high-capacity silicon-based negative electrode materials, the initial cycle coulombic efficiency and the battery capacity of the battery are low. Lithium metal is used for lithium supplementation of active lithium at the negative electrode, which is currently considered as one means of operability.
As an electrolyte, a halide solid-state lithium ion battery has high ionic conductivity and high voltage stability, and is considered as a novel solid-state electrolyte material having both the advantages of an oxide solid-state electrolyte and a sulfide solid-state electrolyte.
However, the halide is extremely unstable to lithium metal, and chemical reaction is easy to occur between the halide and the lithium metal, so that the content of active lithium is reduced, and the lithium supplementing effect is further reduced. Meanwhile, the ionic conductivity of lithium chloride generated by the reaction is lower, so that the overall performance of the battery is reduced in this way.
On the other hand, it has been confirmed that Li is provided on the surface of a silicon-based anode 3 N or Li 3 The P layer is advantageous for improving the battery performance.
Disclosure of Invention
In order to solve one or more of the above-mentioned technical problems in the prior art, embodiments of the present application provide a solid-state lithium ion battery electrode assembly and a solid-state lithium ion battery, so as to solve the problem that the halide of the solid-state electrolyte layer reacts with the lithium metal supplementing layer in the existing solid-state battery, thereby reducing the overall performance of the battery.
In order to solve the above problems, in one aspect, the present application provides a solid-state lithium ion battery, including a positive electrode, a negative electrode, and a composite solid-state electrolyte layer disposed between the positive electrode and the negative electrode, a lithium metal supplementing layer disposed between the solid-state electrolyte layer and the negative electrode, the negative electrode including a negative electrode active material including a silicon-based active material;
the composite solid electrolyte layer comprises a sulfide solid electrolyte layer and a halide solid electrolyte layer which are adjacently arranged; the sulfide solid electrolyte is adjacent to the lithium metal supplementing layer, and the halide solid electrolyte layer is adjacent to the positive electrode;
the sulfide solid electrolyte of the sulfide solid electrolyte layer is Li 6 PS 5 Cl；
The halide solid electrolyte is Li 2 ZrCl 6 ；
Or alternatively, the first and second heat exchangers may be,
the chemical general formula of the halide solid electrolyte layer is as follows: li (Li) 2+e1-f1 Zr 1-e1- f1 A e1 B f1 X 6 The method comprises the steps of carrying out a first treatment on the surface of the The valence state of the element B is 5; the value range of 2+e1-f1 is 1.85-2.45; the value range of e1+f1 is 0.1-0.5, and the value range of e1/f1 is 0.5-3.5; the element A is Ga 3+ 、In 3+ 、Al 3+ 、Fe 3+ 、Y 3+ 、Bi 3+ At least one of the +3 valent lanthanoids;
or alternatively, the first and second heat exchangers may be,
the halide of the halide solid electrolyte layer has a chemical formula of Li 2+e2+2f2 Zr 1-e2-f2 M e2 N f2 Y 6 The element M is selected from Ga 3+ 、In 3+ 、Al 3+ 、Fe 3+ 、Y 3+ 、Bi 3+ At least one of the +3 valent lanthanoids; and the value range of 2+e2+2f2 is 2.15-2.65; the element N is different from the element M, and the ionic radius r (N) of the element N is 60 picometers < r (N) <95 picometers; the value range of e2+f2 is 0.1-0.5, and the value range of e2/f2 is 1-6; y is one or more elements in F, cl, br, l.
Preferably, the halide solid state electrolyte layer includes a third halide layer near one side of the sulfide solid state electrolyte layer, a first halide layer near one side of the positive electrode, and a second halide layer interposed between the first halide layer and the third halide layer;
the first halide layer comprises a first halide electrolyte material and the second halide layer comprises a second halide electrolyte material; the third halide layer includes a third halide electrolyte material:
the first halide electrolyte material has the chemical formula of Li 2+a1+2b1 Zr 1-a1-b1 M a1 N b1 Cl c1 F d1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c1+d1= 6,0.1 is less than or equal to d1 and less than or equal to 0.5, the value range of a1+b1 is 0.1-0.5, and the value range of a1/b1 is 1-6;
the second halide electrolyte material has a chemical formula of Li 2+a2+2b2 Zr 1-a2-b2 M a2 N b2 Cl c2 I d2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c2+d2= 6,0.2 is less than or equal to d2 and less than or equal to 1.2, the value range of a2+b2 is 0.1-0.5, and the value range of a2/b2 is 1-6;
the chemical formula of the third halide electrolyte material is Li 2+a3+2b3 Zr 1-a3-b3 M a3 N b3 Cl c3 F d3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c3+d3= 6,0.03 is less than or equal to d3 and less than or equal to 0.08, the value range of a3+b3 is 0.1-0.5, and the value range of a3/b3 is 1-6;
the ionic radius r (M) of the element M and the ionic radius r (N) of the element N in the first, second and third halide electrolyte materials satisfy 0.6< r (N)/r (M) <1.05;
the element N is at least one of Co, cu, zn, mg, cd;
the element M is selected from one or two of Eu and Gd.
Preferably, the thickness of the lithium metal supplementing layer is 1-20 μm.
Preferably, the thickness of the sulfide solid state electrolyte layer is 10 to 20% of the thickness of the halide solid state electrolyte layer.
Preferably, the silicon-based active material is elemental silicon or comprises a lithium silicon alloy.
The beneficial effects are that:
the solid lithium ion battery provided by the application adds a chemical formula Li containing phosphorus element between the halide electrolyte layer and the metal lithium supplementing layer on the premise of adopting the halide with high ion conductivity as the electrolyte and adopting the metal lithium as the lithium supplementing layer to supplement lithium 6 PS 5 The sulfide solid state electrolyte layer of Cl avoids undesirable side reactions between metallic lithium and halide solid state electrolytes; at the same time Li 6 PS 5 The lithium phosphide generated by the reaction of Cl and metal lithium is coated on the silicon-based cathode, which is beneficial to improving the transmission capacity of lithium ions in the batteryImproving the electrochemical performance. The lithium phosphide has higher ionic conductivity than lithium chloride generated by halide and metal lithium, and has low grain boundary resistance, good reduction stability and high ion selectivity; can meet the ion conduction of a solid lithium battery, can not further react with lithium metal to generate a product with low ion conductivity, and has the effect of inhibiting lithium dendrite. The application utilizes the reaction of the lithium metal supplementing layer and the sulfide solid electrolyte layer, solves the interface reaction problem of the halide solid electrolyte and the lithium metal, improves the performance of the silicon negative electrode, improves the cycle performance and the multiplying power performance of the silicon negative electrode, and improves the first cycle performance of the battery.
Drawings
Fig. 1 is a schematic diagram of a solid-state lithium ion battery.
Detailed Description
Aiming at the problems caused by the easy reaction of halide and metal lithium in the scheme of adopting a silicon-based anode with higher specific energy, metal lithium supplementing lithium and adopting halide as a solid electrolyte material in the prior art, the application creatively adds a sulfide solid electrolyte layer containing phosphorus between the halide solid electrolyte layer and the metal lithium supplementing lithium layer, and improves the performance of the battery by virtue of the characteristics of difficult reaction of sulfide with the metal lithium and low interface resistance between the sulfide and the halide. More excellent is that in the scheme, the lithium phosphide generated by the self-limiting reaction of the phosphorus sulfide and the metal lithium is covered on the silicon-based negative electrode, so that the transmission capacity of lithium ions in the composite silicon-based negative electrode can be improved, the rate performance of the composite silicon-based negative electrode can be improved, and the problems of low ion conductivity, poor rate performance and poor cycle performance of the silicon-based negative electrode are solved; the generated lithium phosphide has higher ion conductivity than lithium chloride generated by halide and metal lithium, has low grain boundary resistance, good reduction stability and high ion selectivity, and can meet the ion conduction of a solid-state lithium battery; and lithium phosphide can not further react with lithium metal to generate a product with low ionic conductivity, and has the effect of inhibiting lithium dendrites. In summary, this approach ensures lithium supplementation effect, high ionic conductivity, low resistance and high interfacial stability, and simultaneously improves the overall performance of the battery such as rate, cycle, etc.
The embodiment of the application provides a novel solid-state lithium ion battery, as shown in fig. 1, specifically comprising a negative electrode 11, a lithium metal supplementing layer 12 and a composite solid-state electrolyte layer, which are sequentially stacked on the negative electrode 11, and a positive electrode 15, wherein the composite solid-state electrolyte layer comprises a sulfide solid-state electrolyte layer 13 containing phosphorus and a halide solid-state electrolyte layer 14. The sulfide solid electrolyte layer 13 is adjacent to the lithium metal supplementing layer 12, the halide solid electrolyte layer 14 is adjacent to the positive electrode 15, and a layout structure is formed in which the sulfide solid electrolyte layer 13 is added between the lithium metal supplementing layer 12 and the halide solid electrolyte layer 14 to block the lithium metal supplementing layer. Wherein the anode 11 includes an anode active material including a silicon-based active material. The added sulfide solid electrolyte layer has excellent stability to metal lithium, ensures the content of active lithium, and avoids the reduction of the lithium supplementing effect due to active reaction of halide and metal lithium. In addition, the surface resistance between sulfide and halide is very small and can be almost ignored through research, so that the problem of resistance increase caused by adding a sulfide solid electrolyte layer is avoided. The sulfide is a solid electrolyte with relatively good performance, and compared with the prior art, the sulfide solid electrolyte layer is additionally arranged between the metal lithium supplementing layer and the halide solid electrolyte layer, so that the good characteristics of lithium supplementing effect, high ion conductivity, low resistance and the like are ensured.
In the above embodiments, the silicon-based active material may be elemental silicon or may include a silicon alloy such as a lithium silicon alloy. In some cases it may also be mixed with graphite. The specific energy of silicon is as high as 3579mah/g, which is much higher than the specific energy 372mah/g of carbon. However, the silicon-based material has low ionic conductivity, poor rate capability and poor cycle performance. In the application, lithium phosphide generated by self-limiting reaction between metal lithium and phosphorus sulfide in the sulfide solid electrolyte layer is covered on the silicon negative electrode, which is beneficial to improving the conductivity of lithium ions in the silicon negative electrode and the multiplying power performance of the lithium ions. And the generated lithium phosphide serving as a negative electrode coating substance has certain rigidity, can effectively inhibit the volume change of the negative electrode in the charge and discharge process, and improves the cycle stability of the negative electrode. And the self-limiting reaction between the metal lithium and the sulfide containing phosphorus can generate an interface composed of lithium sulfide, lithium phosphide and lithium chloride, so that a lithium ion interface with good conductive effect is constructed.
In a preferred embodiment, the sulfide in the sulfide solid state electrolyte layer containing phosphorus is Li 6 PS 5 Cl。
It is understood that the thickness of the solid electrolyte layer is not particularly limited in the present application, and that the thickness of the solid electrolyte layer within a known range is within the scope of the present application without departing from the concept of the present application, and is merely illustrative and not limiting, and the thickness of the solid electrolyte layer is 1 to 1000 μm, and more preferably, the thickness of the solid electrolyte layer is 10 to 500 μm;
preferably, the thickness ratio of the sulfide solid state electrolyte layer to the halide solid state electrolyte layer is 0.01 to 1; further preferably, 0.1 to 0.5; more preferably from 0.15 to 0.3, and still more preferably from 0.1 to 0.2.
In a specific embodiment, the thickness of the lithium metal supplementing layer is 1-20 mu m; preferably, the thickness of the lithium metal supplementing layer is 3-10 mu m; the proper lithium supplementing layer thickness can meet the lithium supplementing requirement and simultaneously avoid the safety problem caused by excessive activity of battery metal lithium.
It will be appreciated that the present application is not particularly limited to the form of the lithium metal-supplementing layer, and that known lithium metal-supplementing layers can be used in the present application, such as lithium metal powder or lithium metal foil, without departing from the spirit of the application; as a particularly preferred embodiment, the lithium metal supplementing layer is in direct contact with the negative electrode.
It is understood that the above direct contact means that no additional structure is provided between the lithium metal supplementing layer and the silicon negative electrode, such as an inert layer or a protective layer for preventing the ignition of the lithium metal, etc.
As one embodiment, the metallic lithium of the metallic lithium supplementing layer has an array structure.
It will be appreciated that the array structure can be used to adjust the amount of lithium replenishment and to adjust for safety issues due to excess lithium.
In the embodiment of the present application, the halide solid electrolyte in the halide solid electrolyte layer may be Li 2 ZrCl 6 And or Li 2 ZrCl 6 Doped derivatives. Li (Li) 2 ZrCl 6 The reaction of the lithium ion battery with the lithium metal supplementing layer directly affects the structural stability of the electrolyte layer, and has a great adverse effect on the overall ion conductivity of the battery.
Specifically, the chemical formula of the halide solid electrolyte is: li (Li) 2+e1-f1 Zr 1-e1-f1 A e1 B f1 X 6 The method comprises the steps of carrying out a first treatment on the surface of the The valence state of the element B is 5; the value range of 2+e1-f1 is 1.85-2.45, preferably 2.0-2.3; the value range of e1+f1 is 0.1-0.5, preferably 1-3, and the value range of e1/f1 is 0.5-3.5; the element A is Ga 3+ 、In 3+ 、Al 3+ 、Fe 3+ 、Y 3+ 、Bi 3+ At least one of +3 valent lanthanide metals. The valence state of the element B is 5; element X is at least one of F, cl, br, I.
Or alternatively, the first and second heat exchangers may be,
the chemical formula of the halide solid electrolyte is as follows: li (Li) 2+e2+2f2 Zr 1-e2-f2 M e2 N f2 Y 6 The element M is selected from Ga 3+ 、In 3+ 、Al 3+ 、Fe 3+ 、Y 3+ 、Bi 3+ At least one of the +3 valent lanthanoids; and the value range of 2+e2+2f2 is 2.15-2.65, preferably 2.2-2.45; the element N is different from the element M, and the ionic radius r (N) of the element N is 60 picometers < r (N) <95 picometers; the value range of e2+f2 is 0.1-0.5, and the value range of e2/f2 is 1-6; y is one or more elements in F, cl, br, l.
In one embodiment, the halide solid state electrolyte layer is a multilayer structure including a third halide layer adjacent to one side of the sulfide solid state electrolyte layer, a first halide layer adjacent to the positive electrode side of the solid state lithium ion battery, and a second halide layer interposed between the first halide layer and the third halide layer; the first halide layer comprises a first halide electrolyte material and the second halide layer comprises a second halide electrolyte material; the third halide layer includes a third halide electrolyte material:
the first halide electrolyte material has the chemical formula of Li 2+a1+2b1 Zr 1-a1-b1 M a1 N b1 Cl c1 F d1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c1+d1= 6,0.1 is less than or equal to d1 and less than or equal to 0.5, the value range of a1+b1 is 0.1-0.5, and the value range of a1/b1 is 1-6;
the second halide electrolyte material has a chemical formula of Li 2+a2+2b2 Zr 1-a2-b2 M a2 N b2 Cl c2 I d2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c2+d2= 6,0.2 is less than or equal to d2 and less than or equal to 1.2, the value range of a2+b2 is 0.1-0.5, and the value range of a2/b2 is 1-6;
the thickness of the second halide layer is at least 85% of the thickness of the entire solid state electrolyte structure;
the chemical formula of the third halide electrolyte material is Li 2+a3+2b3 Zr 1-a3-b3 M a3 N b3 Cl c3 F d3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c3+d3= 6,0.03 is less than or equal to d3 and less than or equal to 0.08, the value range of a3+b3 is 0.1-0.5, and the value range of a3/b3 is 1-6;
the element N is different from the element M, and an ionic radius r (N) of the element N is 60 picometers < r (N) <95 picometers; the ionic radius r (M) of the element M and the ionic radius r (N) of the element N in the first, second and third halide electrolyte materials satisfy 0.6< r (N)/r (M) <1.05; the element N is at least one of Co, cu, zn, mg, cd; the element M is selected from one or two of Eu and Gd.
In the embodiment, the first halide layer is doped with F, so that the material has better electrochemical stability for the anode material with a wide electrochemical window; meanwhile, as the I doping has a remarkable improvement effect on the ionic conductivity of the halide solid electrolyte designed by the application, the application takes the halide solid electrolyte doped with iodine as the main material in the second halide layer, and improves the overall ionic conductivity.
In one embodiment, the halide solid electrolyte layer further includes a binder, the kind of which is not particularly limited, any known kind of binder suitable for the halide solid electrolyte can be used in the present application without departing from the concept of the present application, and the binder may be selected from one or more of styrene butadiene block polymer, styrene butadiene styrene block polymer, styrene thermoplastic elastomer, styrene butadiene rubber, natural rubber, isoprene rubber, ethylene-propylene-diene terpolymer, and silicone resin by way of illustrative example only, and not limitation of the scope of protection.
The present application is not particularly limited to the positive electrode, and the positive electrode is generally composed of a positive electrode current collector and a positive electrode active material layer. The positive electrode current collector is generally composed of a conductive metal foil, and illustrative examples include copper foil, aluminum foil, stainless steel, and the like; the positive electrode active material layer is generally composed of a positive electrode active material including but not limited to LiCoO, a conductive agent, and a binder 2 、LiMnO 2 、LiNiO 2 、LiVO 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiMn 2 O 4 、LiTi 5 O 12 、Li(Ni 0.5 Mn 1.5 )O 4 、LiFePO 4 、LiMnPO 4 、LiNiPO 4 、LiCoPO 4 、LiNbO 3 Or a sulfur-carbon composite material, or a combination of any one or at least two thereof. Wherein LiCoO 2 、LiMnO 2 、LiNiO 2 、LiVO 2 And LiNi 1/3 Co 1/3 Mn 1/3 O 2 Has a rock salt lamellar structure, liMn 2 O 4 、LiTi 5 O 12 And Li (Ni) 0.5 Mn 1.5 )O 4 Has spinel structure, liFePO 4 、LiMnPO 4 、LiNiPO 4 、LiCoPO 4 And LiNbO 3 Has an olivine structure. Any known positive electrode active material can be used in the present application without departing from the concept of the present application.
The positive electrode active material layer is optionally mixed with a binder: such as Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, or combinations thereof. Meanwhile, the positive electrode active material layer may optionally be added with a conductive agent to provide a conductive path, and the conductive agent may include a carbon-based material, powdered nickel or other metal particles, or a conductive polymer. Examples of the conductive polymer include polyaniline, polythiophene, polyacetylene, polypyrrole, and the like.
The surface of the positive electrode active material may also be coated with a coating layer for the purpose of inhibiting the reaction of the positive electrode active material with the electrolyte or improving the ion transport efficiency of the entire positive electrode.
In some embodiments, the coating of the surface of the positive electrode active material is a solid electrolyte coating, such as lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, or a combination of a solid electrolyte and a lithium salt, including but not limited to LiPF 6 、LiBF 4 、LiCLO 4 、LiAsF 6 、LiCF 3 SO 3 Or LiN (CF) 3 SO 2 ) 2 One or more of them.
In some embodiments, the outer coating of the positive electrode active material is a ceramic particle coating, such as SiO 2 、Al 2 O 3 、TiO 2 Etc.
In some embodiments, the coating of the surface of the positive electrode active material is a carbon coating, amorphous carbon, graphene, graphite, or the like.
As an illustrative example, the negative electrode of the present application includes a negative electrode current collector and a negative electrode active material layer including a negative electrode active material that is a silicon-based negative electrode active material that includes silicon, such as elemental silicon, a silicon alloy, or other silicon-containing combinations, which may also be mixed with graphite in some cases.
Hereinafter, embodiments of the present application will be described more specifically by way of examples, and the present application and effects will be described in more detail. However, embodiments of the present application are not limited to these examples only.
Preparation of positive electrode: mixing NCM811, PVDF and super-P in a mass ratio of 95:3:2 in a solvent NMP, and uniformly stirring to obtain positive electrode slurry; coating the positive electrode slurry on the surface of an aluminum foil, drying, cold pressing, cutting and slitting to prepare a positive electrode plate;
preparation of the negative electrode: mixing a negative electrode active material, (CMC+SBR) and super-P in deionized water according to a mass ratio of 94:4:2, and uniformly stirring to obtain a negative electrode slurry; coating the negative electrode slurry on the surface of a copper foil, drying, cold pressing, cutting and slitting to prepare a negative electrode plate;
preparation of halides: the halide solid electrolyte material was mixed with the binder PTFE according to 90:10, and then pressing into a film;
preparation of sulfides: sulfide solid electrolyte material and binder PTFE were mixed according to 90:10, and then pressing into a film;
preparation of a lithium supplementing layer: lithium foil with a thickness of 5 μm;
solid-state lithium battery assembly: and sequentially laminating and assembling the positive plate, the halide film, the sulfide film, the lithium foil and the negative plate to obtain the solid-state lithium ion battery.
Wherein the specific choices of the negative electrode, sulfide film, and halide film are as follows in table 1:
TABLE 1
In order to strongly support the beneficial effects brought by the technical solutions of the embodiments of the present application, electrochemical performance tests were performed on each of the solid-state lithium batteries of the comparative examples and the embodiments in table 1, and the test results are summarized in table 2 below.
The test method is as follows:
ion conductivity test: the symmetrical blocking cell SS/CSE/SS measurement system was assembled in an argon filled glove box. The electrochemical workstation is used for measuring the alternating current impedance at 30 ℃, the alternating current perturbation amplitude is 5mV, and the frequency range is 100 KHz-1 Hz.
Cell resistance test: the prepared battery can measure the internal resistance through a voltage internal resistance meter.
Testing the battery multiplying power: the gram capacity of the prepared cells at 0.1C, 0.2C, 0.5C, 1C were tested at a temperature of 25 ℃ and a voltage interval of 2.0-4.6V.
First coulombic efficiency:
the first circle coulombic efficiency was tested using an electrochemical workstation at 0.1C charge and 0.1C discharge.
And (3) testing the cycle performance:
and (3) carrying out cycle performance test on the assembled battery on a battery workstation, wherein the voltage range is 3-4.25V, the test temperature is 25 ℃, the first two cycles adopt small multiplying power of 0.05C, the multiplying power is adjusted to 0.2C from the third cycle, the capacity after 100 cycles is recorded, and the 100 th cycle capacity is divided by the 3 rd cycle capacity to obtain the cycle capacity retention rate.
TABLE 2
As is apparent from comparison of examples and comparative examples, the provision of the sulfide solid electrolyte layer between the halide solid electrolyte layer and the metal lithium supplemental lithium layer effectively solves the interaction between metal lithium and halide, making it possible to use the halide solid electrolyte in the solid-state battery including the metal lithium supplemental lithium layer.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.

Claims (5)

1. The solid-state lithium ion battery is characterized by comprising a positive electrode, a negative electrode and a composite solid-state electrolyte layer, wherein the composite solid-state electrolyte layer is arranged between the positive electrode and the negative electrode, a metal lithium supplementing lithium layer is arranged between the composite solid-state electrolyte layer and the negative electrode, the negative electrode comprises a negative electrode active material, and the negative electrode active material comprises a silicon-based active material;
the composite solid electrolyte layer comprises a sulfide solid electrolyte layer and a halide solid electrolyte layer which are adjacently arranged; the sulfide solid electrolyte layer is adjacent to the lithium metal supplementing layer, and the halide solid electrolyte layer is adjacent to the positive electrode;
the sulfide solid electrolyte in the sulfide solid electrolyte layer is Li 6 PS 5 Cl；
The halide solid electrolyte in the halide solid electrolyte layer is Li 2 ZrCl 6 ；
Or alternatively, the first and second heat exchangers may be,
the chemical general formula of the halide solid electrolyte in the halide solid electrolyte layer is as follows: li (Li) 2+e1-f1 Zr 1-e1- f1 A e1 B f1 X 6 The method comprises the steps of carrying out a first treatment on the surface of the The valence state of the element B is 5; the value range of 2+e1-f1 is 1.85-2.45; the value range of e1+f1 is 0.1-0.5, and the value range of e1/f1 is 0.5-3.5; the element A is Ga 3+ 、In 3+ 、Al 3+ 、Fe 3+ 、Y 3+ 、Bi 3+ At least one of the +3 valent lanthanoids;
or alternatively, the first and second heat exchangers may be,
the chemical formula of the halide solid electrolyte in the halide solid electrolyte layer is Li 2+e2+2f2 Zr 1-e2- f2 M e2 N f2 Y 6 The element M is selected from Ga 3+ 、In 3+ 、Al 3+ 、Fe 3+ 、Y 3+ 、Bi 3+ At least one of the +3 valent lanthanoids; and the value range of 2+e2+2f2 is 2.15-2.65; the element N is different from the element M, and the ionic radius r (N) of the element N is 60 picometers < r (N) <95 picometers; the value range of e2+f2 is 0.1-0.5, and the value range of e2/f2 is 1-6; y is one or more elements in F, cl, br, l.
2. The solid state lithium ion battery of claim 1, wherein the halide solid state electrolyte layer comprises a third halide layer adjacent to a side of the sulfide solid state electrolyte layer, a first halide layer adjacent to the positive electrode side, and a second halide layer between the first halide layer and the third halide layer;
the first halide layer comprises a first halide electrolyte material and the second halide layer comprises a second halide electrolyte material
Dihalide electrolyte materials; the third halide layer includes a third halide electrolyte material:
the first halide electrolyte material has the chemical formula of Li 2+a1+2b1 Zr 1-a1-b1 M a1 N b1 Cl c1 F d1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c1+d1= 6,0.1 is less than or equal to d1 and less than or equal to 0.5, the value range of a1+b1 is 0.1-0.5, and the value range of a1/b1 is 1-6;
the second halide electrolyte material has a chemical formula of Li 2+a2+2b2 Zr 1-a2-b2 M a2 N b2 Cl c2 I d2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c2+d2= 6,0.2 is less than or equal to d2 and less than or equal to 1.2, the value range of a2+b2 is 0.1-0.5, and the value range of a2/b2 is 1-6;
the chemical formula of the third halide electrolyte material is Li 2+a3+2b3 Zr 1-a3-b3 M a3 N b3 Cl c3 F d3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, c3+d3= 6,0.03 is less than or equal to d3 and less than or equal to 0.08, the value range of a3+b3 is 0.1-0.5, and the value range of a3/b3 is 1-6;
the ionic radius r (M) of the element M and the ionic radius r (N) of the element N in the first, second and third halide electrolyte materials satisfy 0.6< r (N)/r (M) <1.05;
the element N is at least one of Co, cu, zn, mg, cd;
the element M is selected from one or two of Eu and Gd.
3. The solid state lithium ion battery of claim 1, wherein the lithium metal supplementing layer has a thickness of 1-20 μm.
4. The solid state lithium ion battery of claim 1, wherein the sulfide solid state electrolyte layer has a thickness of 10-20% of the thickness of the halide solid state electrolyte layer.
5. The solid state lithium-ion battery of any of claims 1-4, wherein the silicon-based active material is elemental silicon or comprises a lithium-silicon alloy.
CN202311117548.XA 2023-09-01 2023-09-01 Solid lithium ion battery Pending CN116845393A (en)

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