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CN118472358A - Novel battery based on composite solid electrolyte and organic lithium negative electrode - Google Patents

Novel battery based on composite solid electrolyte and organic lithium negative electrode Download PDF

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Publication number
CN118472358A
CN118472358A CN202410915297.8A CN202410915297A CN118472358A CN 118472358 A CN118472358 A CN 118472358A CN 202410915297 A CN202410915297 A CN 202410915297A CN 118472358 A CN118472358 A CN 118472358A
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lithium
electrolyte
solid electrolyte
composite
negative electrode
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伍登旭
朱磊
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Liyang Zhongke Guneng New Energy Technology Co ltd
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Liyang Zhongke Guneng New Energy Technology 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
    • H01M10/05—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a novel battery based on a composite solid electrolyte and an organic lithium negative electrode, and relates to the field of lithium metal battery preparation. According to the invention, firstly, the organic-inorganic composite electrolyte structure design is adopted, on one hand, a layer of ultrathin polymer/gel layer can be introduced on the surface of the inorganic solid electrolyte through surface engineering, so that the inorganic solid electrolyte has excellent ionic conductivity and compactness, and good physical contact and chemical stability with anode and cathode materials are realized; on the other hand, the novel inorganic-polymer homogeneous composite electrolyte membrane can be prepared by a wet process, and has flexibility and compactness; the organic lithium liquid is introduced into the negative side, so that nucleation and growth of lithium dendrites can be fundamentally inhibited, and stable long circulation is realized. The novel quasi-solid state battery prepared by the invention avoids the problems that the traditional all-solid state battery needs to be assembled in a die cell and needs to circulate under high pressure, and realizes the effect of stable circulation under room temperature.

Description

Novel battery based on composite solid electrolyte and organic lithium negative electrode
Technical Field
The invention relates to the technical field of lithium metal battery preparation, in particular to a novel battery based on a composite solid electrolyte and an organic lithium negative electrode.
Background
Conventional commercial lithium secondary batteries mostly use a liquid electrolyte. However, it faces an upper "bottleneck" of 350Wh/kg in terms of energy density, and presents a safety hazard such as thermal runaway. However, compared with inflammable organic liquid electrolyte, the solid electrolyte has the characteristics of high thermal stability, non-inflammability, no leakage, non-volatilization and the like, and is beneficial to improving the safety and stability of the battery. Meanwhile, the use of the solid electrolyte enables the application of the metallic lithium anode, thereby improving the energy density of the battery, so that research on the solid electrolyte becomes a hot spot direction at present and in the future. The solid electrolyte system mainly comprises three types of polymers, oxides and sulfides, wherein the sulfide solid electrolyte has the advantages of highest ionic conductivity, better mechanical ductility and the like, and is one of the very promising technical routes for developing all-solid-state lithium batteries.
However, recent studies have shown that the high mechanical strength of the solid electrolyte cannot completely and effectively suppress lithium dendrites, which are still generated in the solid electrolyte when a metallic lithium or Li-Si alloy anode is used, so that the all-solid battery faces problems of large interfacial resistance, short cycle life, small critical current density, and the like. In addition, solid-solid contact between the solid electrolyte and the solid anode and the solid cathode is continuously deteriorated, and interface stability is continuously deteriorated, further impeding practical application of the all-solid battery. To solve these problems, researchers have improved solid-solid contact and suppressed diffusion of lithium dendrites in the electrolyte by optimizing the solid electrolyte composition and forming an artificial electrolyte layer at the interface, and the like. However, based on the current battery structure system, the interface instability between the solid electrolyte and the solid anode and the solid cathode is always present, so that it is difficult to fundamentally solve the problem. In addition, current polymer electrolyte based batteries require higher temperatures (> 50 ℃) to operate because the polymer electrolyte room temperature conductivity is at the bottom. However, most of solid-state batteries based on inorganic solid-state electrolytes need to operate under a large pressure (tens to hundreds of megapascals), which makes the practical application of such batteries very problematic, and it is of great importance to develop solid-state batteries with high safety and high energy density that can operate at normal temperature and normal pressure.
In summary, we propose a new battery based on a composite solid electrolyte and an organolithium negative electrode, the battery electrolyte adopts a composite electrolyte of an inorganic solid electrolyte and a polymer/gel electrolyte, and the organolithium negative electrode is introduced at the negative electrode side to break through the inherent limitations of the existing liquid lithium battery and solid lithium battery.
Disclosure of Invention
The invention aims to provide a novel battery based on a composite solid electrolyte and an organic lithium negative electrode, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a novel battery based on a composite solid electrolyte and an organic lithium negative electrode, which sequentially comprises the organic lithium composite negative electrode, an inorganic solid electrolyte, a polymer/gel electrolyte composite solid electrolyte and a solid positive electrode from the negative electrode to the positive electrode; the organic lithium composite negative electrode is prepared from an organic lithium solution and porous foam nickel; the organic lithium solution is prepared by mixing metal lithium, aromatic hydrocarbon and ether liquid according to a certain proportion; the aromatic hydrocarbon includes: one or more of anthracene, phenanthrene, naphthalene, biphenyl; the ether liquid comprises one or more of diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, dipropyl ether, diisopropyl ether, ethylbutyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dioxolane, 1, 4-dioxane, ethylene oxide, propylene oxide and 1, 1-diethoxyethane.
Further, the total conductivity of the organic lithium solution is not lower than 1mS/c; a certain amount of lithium source can be added into the organic lithium to improve the theoretical specific capacity of the composite negative electrode, wherein the lithium source comprises one or more of metal lithium and lithium alloy; the lithium alloy includes one or more of lithium silicon, lithium zinc, or lithium silver.
Further, the inorganic solid electrolyte comprises sulfide electrolyte and oxide electrolyte, and the ionic conductivity at room temperature is more than 1 mS/cm; wherein the sulfide electrolyte is selected from any one or more of Li3PS4、Li10GeP2S12、Li7P3S11、Li6PS5Cl 、Li9.54Si1.74P1.44S11.7Cl0.3、Li4SnS4、Li3.85Sn0.85Sb0.15S4、Li3.8Sn0.8As0.2S4、Li4Sn0.9Si0.1S4、Li10SnP2S12、Li7GePS8、Li3.25Ge0.25P0.75S4、Li3.25P0.95S4、Li11Si2PS12、Li7P2S8I、Li8P2S9、80(0.7Li2S·0.3P2S5)·20LiI、95（0.8Li2S·0.2P2S5）5LiI、56Li2S·24P2S5·20Li2O、75Li2S·21P2S5·4P2O5、33(0.7B2S3·0.3P2S5)·67Li2S、67(0.75Li2S·0.25P2S5)·33LiBH4; the oxide electrolyte is selected from one or more of lanthanum lithium titanate （LLTO）,Li1+6xM4+ 2−xM′3+ x (PO4)3 (M = Ti, Ge, Sn, Hf, or Zr; M′= Al, Cr, Ga, Sc, Y, In, La), Li16−2xMx(TO4)4 (M = Mg, Zn; T = Si, Ge), Li7−xLa3Zr2−xMxO12(M= Ta, Al, Ga, Nb, W).
Further, the mass percentage of the polymer/gel electrolyte in the composite solid electrolyte is 1% -90%.
Further, the inorganic solid electrolyte and polymer/gel battery composite mode is as follows: the polymer/gel electrolyte is adhered to the inorganic solid electrolyte sheet in the form of an independent film layer to form a multi-layer electrolyte, or the polymer/gel electrolyte and the inorganic solid electrolyte are fully mixed to form a single-layer composite electrolyte; the composite solid electrolyte is in a film shape or a sheet shape, and the thickness of the composite solid electrolyte is between 10 and 1000 mu m.
Further, the polymer/gel electrolyte is a polymer material and lithium salt, and the polymer material comprises one or more of polyethylene oxide (PEO), polyethylene glycol (PEG), poly (ethylene glycol) dimethyl ether (PEGDME), polypropylene oxide (PPO), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF); the gel is a polymer monomer and lithium salt, wherein the polymer monomer comprises one or more of 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, fluoroethylene carbonate, methyl methacrylate and polyethylene glycol diacrylate; the lithium salt comprises one or more of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiWSI), lithium trifluoromethane sulfonate (LiTof), lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), and lithium perchlorate (LiClO 4); the molar ratio of the polymer to the lithium salt is 1:10-10:1.
Further, the solid state positive electrode includes one or more of Lithium Cobalt Oxide (LCO), lithium iron phosphate (LFP), ternary positive electrode material (NCM), lithium-rich manganese-based material (LMO), tiS 2、FeS2 、TiS2、S、CuS、Li2S、MoS6.
Compared with the prior art, the invention has the following beneficial effects:
The technical scheme provides a novel battery based on a composite solid electrolyte and an organic lithium negative electrode; the novel lithium battery sequentially comprises an organic lithium composite negative electrode, a composite solid electrolyte and a solid positive electrode from the negative electrode to the positive electrode; and (3) injection: the battery model is only one specific application scheme under the design scheme, the model is not used for limiting the invention, and any modification, equivalent replacement, improvement and the like which are made within the design thought of the invention are included in the protection scope of the invention;
The liquid lithium anode can solve the problems of poor contact and unstable interface between the solid electrolyte and the solid anode in the traditional all-solid-state battery system, has excellent lithium dissolving performance, and can fundamentally inhibit nucleation and growth of lithium dendrites; the reported liquid lithium comprises materials such as molten alkali metal, fusible liquid alloy and the like, however, the molten alkali metal such as the molten lithium needs an ultra-high working temperature (> 200 ℃), and the high reactivity of the molten lithium can bring serious safety risks; in addition, solidification of fusible liquid alloys (e.g., na-K alloys) may occur during cyclic testing, resulting in delamination and capacity fade of the liquid metal anode; the other novel conductive liquid lithium material is an organic alkali metal aromatic complex, and has the advantages of low cost, low potential (0.2V-0.4V vs. Li +/Li), wide working temperature range (-20-80 degrees), high safety, high ion/electron conductivity and the like;
The organic lithium negative electrode is composed of lithium-aromatic hydrocarbon-ether liquid, and an inorganic lithium source such as lithium silicon alloy is further introduced into the organic lithium negative electrode, so that a composite negative electrode with high specific capacity can be prepared, and the theoretical specific capacity of the composite negative electrode exceeds 600 mAhg –1; the lithium-aromatic hydrocarbon-ether organic lithium negative electrode has good electron conductivity and ion conductivity, and has the property of dissolving lithium dendrite in an unsaturated state, the organic lithium solution has excellent chemical stability on solid electrolyte such as PEO, uniform and rapid Li + conduction is realized at the interface of the solid electrolyte/organic lithium negative electrode, so that lithium dendrite is difficult to nucleate and grow in the composite negative electrode;
in addition, in the technical scheme, the solid-solid contact and chemical stability of the anode material and the solid electrolyte are improved by introducing a novel polymer/gel material into/on the inorganic solid electrolyte; according to the different composite modes, the organic-inorganic composite electrolyte system is divided into two structures of fig. 1 and 2, so that the battery system can avoid the problem that the traditional all-solid-state battery can be circulated well only by relying on large pressure and high temperature, and the application at room temperature and room pressure is realized.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is an organic/inorganic composite solid electrolyte application model A of the present invention;
FIG. 2 is an organic/inorganic composite solid electrolyte application model B of the present invention;
FIG. 3 is a graph of the long cycle performance of a symmetric battery based on a composite solid state electrolyte and an organolithium negative electrode of the invention;
FIG. 4 is a graph of the long cycle performance of a symmetric battery based on a composite solid electrolyte and a lithium silicon-organolithium composite negative electrode of the invention;
FIG. 5 is a graph of the symmetric cell limiting current density (CCD) test results based on a composite solid-state electrolyte and a lithium silicon-organolithium composite negative electrode of the present invention;
FIG. 6 is a graph of the long cycle performance of a symmetric battery based on a lithium-organolithium composite negative electrode of the invention;
FIG. 7 is a graph of the full cell cycle performance of the present invention based on the configuration of FIG. 1;
fig. 8 is a graph of the full cell cycle performance of the present invention based on the configuration of fig. 2.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1; in the embodiment, a Li 6PS5 Cl sulfide electrolyte is selected as a core lithium-conducting medium, PEO electrolyte thin layers are compounded on two sides of the sulfide electrolyte, an organic lithium negative electrode is composed of lithium/phenanthrene/ethylene glycol dimethyl ether, a button symmetrical battery (namely, the organic lithium negative electrodes are arranged on two sides of the compound solid electrolyte) is assembled on the basis of a battery model shown in fig. 1, and the specific implementation steps are as follows:
(1) Tabletting Li 6PS5 Cl to obtain an electrolyte sheet with the diameter of 15mm and the thickness of 0.6mm, and measuring the ionic conductivity of 5 mS/cm;
(2) Dissolving PEO and LiTFSI in Acetonitrile (ACN), stirring at 25deg.C for 24h, and completely dissolving PEO to form uniform slurry; dripping 40 mu L of the slurry on the two side surfaces of a Li 6PS5 Cl electrolyte sheet, uniformly coating, and baking and drying on a heating table at 200 ℃ to form a PEO composite Li 6PS5 Cl electrolyte sheet;
(3) Dissolving phenanthrene (Phen) in 6ml of ethylene glycol dimethyl ether (DME) to form a transparent Phen-DME solution, dissolving lithium wires in the Phen-DME solution to form a blue-black Li-Phen-DME organolithium solution, and measuring the total conductivity to be 10 mS/cm;
(4) A small amount of organic lithium negative electrodes are carried by utilizing a foam nickel porous current collector and are attached to two sides of the composite solid electrolyte, and a symmetrical battery is assembled;
(5) Symmetric battery charge-discharge cycle data were obtained at 30 ℃ using a blue battery test system with a current density of 0.25 mA/cm 2, as shown in fig. 3;
The initial polarization voltage is smaller and is 0.12V, the battery can be cycled for more than 250 hours under the current density of 0.25 mA/cm 2, the polarization voltage is not obviously increased, and the composite solid electrolyte and the organic lithium cathode have good contact and chemical compatibility, so that the symmetrical battery realizes lower interface impedance and better cycling stability.
Example 2; in the embodiment, li 6PS5 Cl sulfide electrolyte is selected as a core lithium-conducting medium, PEO electrolyte thin layers are compounded on two sides of the sulfide electrolyte, lithium silicon alloy powder and lithium/phenanthrene/ethylene glycol dimethyl ether organic lithium solution are compounded to form a composite negative electrode, a button symmetrical battery (namely, the organic lithium composite negative electrode is arranged on two sides of the composite solid electrolyte) is assembled on the basis of a battery model shown in fig. 1, and the specific implementation steps are as follows:
(1) Tabletting Li 6PS5 Cl to obtain an electrolyte sheet with the diameter of 15mm and the thickness of 0.6mm, and measuring the ionic conductivity of 5 mS/cm;
(2) Dissolving PEO and LiTFSI in Acetonitrile (ACN), stirring at 25deg.C for 24h, and completely dissolving PEO to form uniform slurry; dripping 40 mu L of the slurry on the two side surfaces of a Li 6PS5 Cl electrolyte sheet, uniformly coating, and baking and drying on a heating table at 200 ℃ to form a PEO composite Li 6PS5 Cl electrolyte sheet;
(3) Dissolving phenanthrene (Phen) in 6ml of ethylene glycol dimethyl ether (DME) to form a transparent Phen-DME solution, dissolving lithium wires in the Phen-DME solution to form a blue-black Li-Phen-DME organolithium solution, and measuring the total conductivity to be 10 mS/cm;
(4) Pressing lithium silicon alloy powder into porous foam nickel, dripping a small amount of organic lithium into the porous foam nickel to prepare a lithium silicon/organic lithium composite negative electrode, and attaching the lithium silicon/organic lithium composite negative electrode to two sides of a composite solid electrolyte to assemble a symmetrical battery;
(5) Symmetric battery charge-discharge cycle data were obtained at 30 ℃ using a blue battery test system with a current density of 1.27 mA/cm 2, as shown in fig. 4;
The initial polarization voltage is smaller and is 0.2V, and the lithium ion battery can circulate for more than 800 hours under the high current density of 1.27 mA/cm 2, which shows that the composite solid electrolyte and the organic lithium composite negative electrode have good contact and chemical compatibility, so that the symmetrical battery realizes lower interface impedance and better circulation stability.
Example 3; in the embodiment, li 6PS5 Cl sulfide electrolyte is selected as a core lithium-conducting medium, PEO electrolyte thin layers are compounded on two sides of the sulfide electrolyte, a composite negative electrode is composed of lithium silicon alloy-lithium\phenanthrene\ethylene glycol dimethyl ether, a button symmetrical battery (namely, the two sides of the composite electrolyte are both composite negative electrodes) is assembled on the basis of a battery model shown in fig. 1, and the specific implementation steps are as follows:
(1) Tabletting Li 6PS5 Cl to obtain an electrolyte sheet with the diameter of 15mm and the thickness of 0.6mm, and measuring the ionic conductivity of 5 mS/cm;
(2) Dissolving PEO and LiTFSI in Acetonitrile (ACN), stirring at 25deg.C for 24h, and completely dissolving PEO to form uniform slurry; dripping 40 mu L of the slurry on the two side surfaces of a Li 6PS5 Cl electrolyte sheet, uniformly coating, and baking and drying on a heating table at 200 ℃ to form a PEO composite Li 6PS5 Cl electrolyte sheet;
(3) Dissolving phenanthrene (Phen) in 6ml of ethylene glycol dimethyl ether (DME) to form a transparent Phen-DME solution, dissolving lithium wires in the Phen-DME solution to form a blue-black Li-Phen-DME organolithium solution, and measuring the total conductivity to be 10 mS/cm;
(4) Pressing lithium silicon alloy powder into porous foam nickel, dripping a small amount of organic lithium into the porous foam nickel to prepare a lithium silicon/organic lithium composite negative electrode, and attaching the lithium silicon/organic lithium composite negative electrode to two sides of a composite solid electrolyte to assemble a symmetrical battery;
(5) Carrying out limit current density test on the symmetrical batteries at 30 ℃ by using a blue battery test system, namely carrying out charge-discharge cycle test on all the symmetrical batteries by increasing test current gradually from 0.2 mA current until short circuit occurs or the voltage reaches the safety voltage of a detection instrument, as shown in fig. 5;
Under the test condition that the single cycle time is fixed at 1h, the limit current density of the symmetrical battery is as high as 6 mA/cm 2, and the critical unit area capacity is as high as 3 mAh/cm 2; under the test condition that the capacity of the fixed single circulating surface is 0.16 mAh/cm 2, the limit current density of the symmetrical battery is as high as 13 mA/cm 2; the high critical current density value of the symmetrical battery represents the capability of the battery system for inhibiting the growth of lithium dendrites, and the high critical current density value fully demonstrates that the novel battery technology provided by the invention can obviously inhibit the formation of lithium dendrites and prolong the cycle life.
Example 4; in the embodiment, li 6PS5 Cl sulfide electrolyte is selected as a core lithium-conducting medium, PEO electrolyte thin layers are compounded on two sides of the sulfide electrolyte, a composite negative electrode is composed of lithium sheets-lithium\phenanthrene\ethylene glycol dimethyl ether, a button symmetrical battery (namely, the two sides of the composite electrolyte are both composite negative electrodes) is assembled on the basis of a battery model shown in fig. 1, and the specific implementation steps are as follows:
(1) Tabletting Li 6PS5 Cl to obtain an electrolyte sheet with the diameter of 15mm and the thickness of 0.6mm, and measuring the ionic conductivity of 5 mS/cm;
(2) Dissolving PEO and LiTFSI in Acetonitrile (ACN), stirring at 25deg.C for 24h, and completely dissolving PEO to form uniform slurry; dripping 40 mu L of the slurry on the two side surfaces of a Li 6PS5 Cl electrolyte sheet, uniformly coating, and baking and drying on a heating table at 200 ℃ to form a PEO composite Li 6PS5 Cl electrolyte sheet;
(3) Dissolving phenanthrene (Phen) in 6ml of ethylene glycol dimethyl ether (DME) to form a transparent Phen-DME solution, dissolving lithium wires in the Phen-DME solution to form a blue-black Li-Phen-DME organolithium solution, and measuring the total conductivity to be 10 mS/cm;
(4) Taking porous foam nickel as a current collector, pressing a metal lithium sheet as a lithium source and the porous foam nickel together, dripping a small amount of organic lithium into the foam nickel to prepare an organic lithium composite negative electrode, and then attaching the two composite negative electrodes to two sides of an electrolyte sheet to assemble a symmetrical battery;
(5) Symmetric battery charge-discharge cycle data were obtained at 30 ℃ using a blue battery test system with a current density of 0.254 mA/cm 2, as shown in fig. 6;
The initial polarization voltage is smaller and is 0.3V, and the battery can circulate for approximately 1000 hours under the current density of 0.254 mA/cm 2, which shows that the composite solid electrolyte and the composite anode based on the metal lithium as a lithium source have good contact and chemical compatibility, so that the symmetrical battery realizes lower interface impedance and better circulation stability.
Example 5; in the embodiment, li 6PS5 Cl sulfide electrolyte is selected as a core lithium-conducting medium, a PEO electrolyte thin layer is compounded on the negative electrode side of the sulfide electrolyte, a DOL-LiWSI gel thin layer is compounded on the positive electrode side of the sulfide electrolyte, the composite negative electrode is composed of lithium silicon alloy-lithium\phenanthrene\diethylene glycol dimethyl ether, the positive electrode is a lithium iron phosphate wet pole piece, and a button full battery is assembled by using the battery model shown in fig. 1, and the specific implementation steps are as follows:
(1) Tabletting Li 6PS5 Cl to obtain an electrolyte sheet with the diameter of 15mm and the thickness of 0.6mm, and measuring the ionic conductivity of 5 mS/cm;
(2) Dissolving PEO and LiTFSI in Acetonitrile (ACN), stirring at 25deg.C for 24h, and completely dissolving PEO to form uniform slurry; dripping 40 mu L of the slurry on one side surface of a Li 6PS5 Cl electrolyte sheet, uniformly coating, and baking and drying on a heating table at 200 ℃ to form a PEO-Li 6PS5 Cl electrolyte sheet;
(3) Taking a plurality of DOL liquid, adding LiFeSI salt into the DOL liquid, stirring the DOL liquid for a plurality of hours at room temperature until the DOL liquid becomes very viscous due to polymerization initiated by LiFeSI, uniformly coating 10 mu L of the viscous liquid on the surface of a lithium iron phosphate positive plate, then attaching the positive plate on the surface of a Li 6PS5 Cl electrolyte, and standing for a plurality of hours to wait for full gelation of the DOL-LiFeSI solution;
(4) Phenanthrene (Phen) is dissolved in 6ml of diethylene glycol dimethyl ether (G2) to form a transparent solution, lithium wires are dissolved in the Phen-G2 solution to form a blue-black Li-Phen-G2 organic lithium solution, and the total conductivity is measured to be 6 mS/cm;
(5) Preparing a composite negative electrode by taking porous foam nickel and lithium silicon alloy powder as a lithium source and an organic lithium solution; attaching the composite negative electrode to one side of sulfide electrolyte PEO, and assembling a full cell according to a cell model shown in FIG. 1;
(6) Using a blue battery test system to obtain full battery charge-discharge cycle data at 30 ℃, wherein the battery charge-discharge multiplying power is 0.3C, as shown in figure 7;
The full battery has a first-cycle discharge capacity of 151 mAh/g, a first-cycle coulomb efficiency of 91.6%, and a capacity retention rate of more than 98% after 100 cycles, which indicates that the full battery can realize good cycles at room temperature and room pressure.
Example 6; in the embodiment, li 6PS5 Cl sulfide electrolyte is selected as a core lithium-conducting medium, DOL-LiWSI material and sulfide electrolyte are fully mixed and prepared and dried to prepare sulfide polymer composite electrolyte, a composite negative electrode consists of lithium silicon alloy-lithium\phenanthrene\diethylene glycol dimethyl ether, a positive electrode is a lithium iron phosphate wet pole piece, and a button full battery is assembled by a battery model shown in fig. 2, and the specific implementation steps are as follows:
(1) Taking DOL liquid, adding LiFSI salt and Li 6PS5 Cl electrolyte powder into the DOL liquid, stirring for a plurality of hours at room temperature, uniformly coating the thick slurry on an LFP positive plate after the thick slurry is thick, and vacuum drying for a plurality of hours to prepare the sulfide polymer composite electrolyte membrane supported by an LFP cathode, wherein the thickness of the sulfide polymer composite electrolyte membrane is 200 mu m;
(2) Phenanthrene (Phen) is dissolved in 6ml of diethylene glycol dimethyl ether (G2) to form a transparent solution, lithium wires are dissolved in the Phen-G2 solution to form a blue-black Li-Phen-G2 organic lithium solution, and the total conductivity is measured to be 6 mS/cm;
(3) Preparing a composite negative electrode by taking porous foam nickel as a current collector, lithium silicon alloy powder as a lithium source and an organic lithium solution according to the process shown in 3, attaching the negative electrode to one side of a sulfide-polymer composite electrolyte membrane, and assembling a full battery according to a battery model shown in FIG. 2;
(4) Using a blue battery test system to obtain full battery charge-discharge cycle data at 30 ℃, wherein the battery charge-discharge multiplying power is 0.2C, as shown in figure 8;
the initial circle discharge capacity of the full battery is 160 mAh/g, the initial circle coulomb efficiency is 98%, and the discharge capacity after fifty circles is 125 mAh/g, the coulomb efficiency is kept at 99.9%, which indicates that the full battery can realize good circulation under room temperature and room pressure.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (7)

1. The novel battery based on the composite solid electrolyte and the organic lithium negative electrode is characterized by sequentially comprising the organic lithium composite negative electrode, the inorganic solid electrolyte, the polymer/gel electrolyte composite solid electrolyte and the solid positive electrode from the negative electrode to the positive electrode; the organic lithium composite negative electrode is prepared from an organic lithium solution and porous foam nickel; the organic lithium solution is prepared by mixing metal lithium, aromatic hydrocarbon and ether liquid according to a certain proportion; the aromatic hydrocarbon includes: one or more of anthracene, phenanthrene, naphthalene, biphenyl; the ether liquid comprises one or more of diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, tetrahydrofuran, 1, 3-dioxolane, dipropyl ether, diisopropyl ether, ethylbutyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, 2-methyltetrahydrofuran, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dioxolane, 1, 4-dioxane, ethylene oxide, propylene oxide and 1, 1-diethoxyethane.
2. The novel battery based on a composite solid electrolyte and an organolithium negative electrode according to claim 1, characterized in that the total conductivity of the organolithium solution is not lower than 1mS/c; a certain amount of lithium source can be added into the organic lithium to improve the theoretical specific capacity of the composite negative electrode, wherein the lithium source comprises one or more of metal lithium and lithium alloy; the lithium alloy includes one or more of lithium silicon, lithium zinc, or lithium silver.
3. The novel battery based on a composite solid electrolyte and an organic lithium negative electrode according to claim 1, wherein the inorganic solid electrolyte comprises sulfide electrolyte and oxide electrolyte, and the room temperature ionic conductivity is > 1 mS/cm; wherein the sulfide electrolyte is selected from any one or more of Li3PS4、Li10GeP2S12、Li7P3S11、Li6PS5Cl 、Li9.54Si1.74P1.44S11.7Cl0.3、Li4SnS4、Li3.85Sn0.85Sb0.15S4、Li3.8Sn0.8As0.2S4、Li4Sn0.9Si0.1S4、Li10SnP2S12、Li7GePS8、Li3.25Ge0.25P0.75S4、Li3.25P0.95S4、Li11Si2PS12、Li7P2S8I、Li8P2S9、80(0.7Li2S·0.3P2S5)·20LiI、95（0.8Li2S·0.2P2S5）5LiI、56Li2S·24P2S5·20Li2O、75Li2S·21P2S5·4P2O5、33(0.7B2S3·0.3P2S5)·67Li2S、67(0.75Li2S·0.25P2S5)·33LiBH4; the oxide electrolyte is selected from one or more of lanthanum lithium titanate （LLTO）,Li1+6xM4+ 2−xM′3+ x (PO4)3 (M = Ti, Ge, Sn, Hf, or Zr; M′= Al, Cr, Ga, Sc, Y, In, La), Li16−2xMx(TO4)4 (M = Mg, Zn; T = Si, Ge), Li7−xLa3Zr2−xMxO12(M= Ta, Al, Ga, Nb, W).
4. The novel battery based on the composite solid electrolyte and the organic lithium negative electrode, according to claim 1, wherein the mass percentage of the polymer/gel electrolyte in the composite solid electrolyte is 1% -90%.
5. The novel battery based on composite solid electrolyte and organic lithium negative electrode according to claim 1, wherein the inorganic solid electrolyte and polymer/gel battery composite mode is: the polymer/gel electrolyte is adhered to the inorganic solid electrolyte sheet in the form of an independent film layer to form a multi-layer electrolyte, or the polymer/gel electrolyte and the inorganic solid electrolyte are fully mixed to form a single-layer composite electrolyte; the composite solid electrolyte is in a film shape or a sheet shape, and the thickness of the composite solid electrolyte is between 10 and 1000 mu m.
6. The novel battery based on a composite solid electrolyte and an organolithium negative electrode according to claim 5, wherein the polymer/gel electrolyte is a polymer material and a lithium salt, the polymer material comprising one or more of polyethylene oxide (PEO), polyethylene glycol (PEG), poly (ethylene glycol) dimethyl ether PEGDME, polypropylene oxide (PPO), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF); the gel is a polymer monomer and lithium salt, wherein the polymer monomer comprises one or more of 1, 3-dioxolane, 1, 3-dioxane, 1, 4-dioxane, fluoroethylene carbonate, methyl methacrylate and polyethylene glycol diacrylate; the lithium salt comprises one or more of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiWSI), lithium trifluoromethane sulfonate (LiTof), lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), and lithium perchlorate (LiClO 4); the molar ratio of the polymer to the lithium salt is 1:10-10:1.
7. The novel battery based on a composite solid electrolyte and an organic lithium negative electrode according to claim 1, wherein the solid positive electrode comprises one or more of Lithium Cobalt Oxide (LCO), lithium iron phosphate (LFP), ternary positive electrode material (NCM), lithium-rich manganese-based material (LMO), tiS 2、FeS2 、TiS2、S、CuS、Li2S、MoS6.
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