CN113690434A - Sulfide material with mixed conduction of electrons and alkali metal ions and application thereof - Google Patents

Sulfide material with mixed conduction of electrons and alkali metal ions and application thereof Download PDF

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CN113690434A
CN113690434A CN202110742401.4A CN202110742401A CN113690434A CN 113690434 A CN113690434 A CN 113690434A CN 202110742401 A CN202110742401 A CN 202110742401A CN 113690434 A CN113690434 A CN 113690434A
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solid
alkali metal
site
sulfide material
sulfide
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董甜甜
任金兰
崔浩然
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Qingdao Zhongkesai Lida New Energy Technology Partnership LP
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention belongs to the technical field of batteries, and relates to a sulfide material for mixed conduction of electrons and alkali metal ions and application thereof in an all-solid-state secondary lithium battery. Sulfide materials of the general formula AMS2Or ATi2(PS4)3In the general formula, A-site and/or S-site aliovalent elements are doped; wherein, A site is alkali metal element, and A site aliovalent doping element is valence>+1 metal element, S-site aliovalent doping element is halogen, M is transition metal element. The invention carries out the replacement of aliovalent elements on the sulfide material containing alkali metal elements and transition metal elements, and further regulates and controls the concentration of alkali metal ions to improve the alkali metal ion conductivity of the sulfide material so as toAnd the valence state of the transition metal element to improve the electron conduction capability of the sulfide material. The sulfide material has an electron conductivity of not less than 1S cm at room temperature−1The ionic conductivity is not less than 0.1 mS cm−1. The invention also discloses an all-solid-state battery assembled by the sulfide material.

Description

Sulfide material with mixed conduction of electrons and alkali metal ions and application thereof
Technical Field
The invention belongs to the technical field of batteries, and relates to a sulfide material for mixed conduction of electrons and alkali metal ions and application thereof in an all-solid-state secondary lithium battery.
Background
Lithium ion batteries are expected to be used as power batteries of electric vehicles and energy storage batteries of new energy sources such as solar energy and wind energy. The commercial lithium ion battery takes liquid organic matters as electrolyte. The liquid electrolyte (electrolyte) has the advantages of high conductivity, good wettability with the surface of an electrode material and the like, but has a narrow electrochemical window (poor electrochemical stability) and poor thermal stability, only a very thin thermoplastic porous diaphragm is used for separating a positive electrode and a negative electrode, the hidden trouble of internal short circuit exists in the processes of packaging, transportation, charging and discharging of the battery, once the internal short circuit occurs in the battery, the battery is disabled slightly, and the battery is ignited and even exploded seriously. Therefore, the conventional lithium ion battery cannot meet the requirement of the modern society on high safety of the battery. Compared with liquid electrolytes, inorganic ceramic electrolytes have good thermal stability and are not combusted, and the inorganic ceramic electrolytes are used for replacing the liquid electrolytes, so that the problem of safety of lithium ion batteries is fundamentally solved.
Among inorganic ceramic electrolytes, a sulfur-based electrolyte has a high room-temperature conductivity (10)−4～10−2 S cm−1) And excellent mechanical properties, and is more and more favored by scientists in the field of all-solid-state batteries. Thus, all-solid-state batteries based on sulfide electrolytes are widely studied. However, due to the instability of the sulfide electrolyte and the conductive additive (chem. mater. 2016, 28, 8, 2634), the composite positive electrode used in the sulfide electrolyte-based all-solid-state battery generally does not contain the conductive additive, and is "positive active material + sulfide electrolyte". Among them, sulfide electrolyte has almost no electron conductivity (10)−10～10−8 S cm−1) Providing only an ion transport channel; the ionic conductivity and the electronic conductivity of the positive active material are insufficient, so that the rate performance of the sulfide-based all-solid-state battery (at room temperature) is greatly limited
Figure 415059DEST_PATH_IMAGE001
C run). Therefore, the development of the sulfide material with both electron and ion transport capacities applied to the composite electrode can improve the room temperature rate performance of the sulfide-based all-solid-state battery, thereby greatly promoting the commercialization process of the sulfide-based all-solid-state battery.
Disclosure of Invention
In view of the above, the present invention provides an electron-alkali metal ion mixed conduction sulfide material and its application in an all-solid-state secondary lithium battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
an electron and alkali metal ion mixed conductive sulfide material with general formula of AMS2Or ATi2(PS4)3In the general formula, A-site and/or S-site aliovalent elements are doped; wherein, A site is alkali metal element, and A site aliovalent doping element is valence>+1 metal element, S-site aliovalent doping element is halogen, M is transition metal element.
The A-site and/or S-site aliovalent elements in the general formula of the sulfide material are doped, so that the valence state of M or Ti in the general formula is changed, and the A number (A atom number) is changed, namely the general formula is A1−zA'xMS2−yS'yOr A1−zA'xTi2(PS4−yS'y)3Wherein x, y and z satisfy the valence requirement of the general formula, and x and y are not 0, 0 at the same time< z < 1。
The general formula of the sulfide material is A1−zA'xMS2−yS'yWhen the valence of A' is a valence, ax + y< z < 1。
In a further aspect of the present invention,
the material is only in AMS2When the A site is doped, the structural formula A is obtained1─zA'xMS2，ax < z < 1；
The material is only in AMS2When S site is doped, the structural formula A is obtained1─zMS2─yS'y，y < z < 1；
The material is disclosed in AMS2When the A site and the S site are codoped, the structural formula A is obtained1─zA'xMS2─yS'y，y < z - ax，z < 1；
The sulfide material is A1−zA'xTi2(PS4−yS'y)3When the valence of A' is a valence,
the material is only ATi2(PS4)3When the A site is doped, the structural formula A is obtained1─zA'xTi2(PS4)3，z < ax < 1；
The material is only ATi2(PS4)3When S site is doped, the structural formula A is obtained1─zTi2(PS4─yS'y)3，z < 3y ≤ 1；
Said material is at ATi2(PS4)3When the A site and the S site are codoped, the structural formula A is obtained1─zA'xTi2(PS4─yS'y)3，z - ax < 3y ≤ 1，z < 1。
A is one or more of Li, Na and K; m is one or more of Fe, Co, Ti, V and Cr; a' is one or more of Ca, Mg, Sr, Ba and Zn; s' is one or more of F, Cl, Br and I.
The preparation method of the sulfide material comprises the following steps:
AMS2: the raw materials are ball-milled and uniformly mixed at a rotating speed of 200-300 rpm, and then are subjected to heat treatment at 600-750 ℃ for 8-12 hours to obtain the sulfide material.
ATi2(PS4)3: the raw materials are ball-milled and uniformly mixed at a rotating speed of 300-400 rpm, and then are subjected to heat treatment at 250-500 ℃ for 4-8 hours to obtain the sulfide material.
The application of a sulfide material with mixed conduction of electrons and alkali metal ions, wherein the sulfide material is applied as a conduction aid.
An all-solid-state secondary lithium battery comprises a positive electrode, a negative electrode and an all-solid-state electrolyte between the positive electrode and the negative electrode, wherein the positive electrode or/and the negative electrode contains the electronic and alkali metal ion mixed conductive sulfide material.
The positive electrode also comprises a positive active material, wherein the positive active material is lithium cobaltate, lithium iron phosphate, lithium manganese oxide, lithium nickel manganese oxide, a ternary material, ferric phosphate salt or ferric manganese phosphate salt, and the electrolyte material is 80Li2S : 20P2S5；Li9+x-yMxP3-xS12-yXyWherein X is more than or equal to 0 and less than or equal to 2, M is one or more of Si, Ge, Sn and Pb, y is more than or equal to 0 and less than or equal to 1, and X is one or more of F, Cl, Br and I; li6PS5X and X are one or more of F, Cl, Br and I; 75Li2S : 25P2S5；Li3PS4；70Li2S : 30P2S5And Li7P3P11One or more of the above; the negative electrode also comprises a negative electrode active material, wherein the negative electrode active material is a metal lithium sheet, a metal lithium alloy, a metal indium sheet, graphite, hard carbon, lithium titanate, graphene or silicon carbon negative electrode.
A method for preparing an all-solid-state secondary lithium battery comprises the steps of laminating a positive electrode, an all-solid-state electrolyte and a negative electrode or the order of the negative electrode, the all-solid-state electrolyte and the positive electrode to form the integrated all-solid-state secondary lithium battery with a sandwich structure.
Compared with the prior art, the invention has the following beneficial effects:
the method can regulate the concentration of alkali metal ions and the valence state of the transition metal element by substituting the aliovalent elements for the sulfide material containing the alkali metal element and the transition metal element, so that the alkali metal ion conductivity of the sulfide material and the electron conductivity of the sulfide material can be improved. The sulfide material has an electron conductivity of not less than 1S cm at room temperature−1The ionic conductivity is not less than 0.1 mS cm−1. The sulfide material with mixed conduction of electrons and alkali metal ions has the ionic conductivity of 10 at 25 DEG C−4～10−3 S cm−1Comparable to the ionic conductivity of sulfide electrolytes; the electronic conductivity is 1-10S cm−1The electronic conductivity of the electrolyte is improved by 9-10 orders of magnitude compared with that of sulfide electrolyte.
Drawings
FIG. 1 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 10.79Ba0.1CrS2An XRD pattern of (a);
fig. 2 is a schematic view of a method for measuring electron conductivity. 1 is a stainless steel electrode, and 2 is a sulfide material with mixed conduction of electrons and alkali metal ions;
fig. 3 is a schematic view of a method for measuring ionic conductivity. 1 is a stainless steel electrode, 2 is metal such as Li, Na, K, In, Sn, 3 is an alkali metal ion conductive material, and 4 is a sulfide material with mixed conduction of electrons and alkali metal ions.
FIG. 4 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 10.79Ba0.1CrS2With lithium cobaltate (LiCoO)2) Composite positive electrode after mixing, Li6PS5Room temperature multiplying power and cycle performance of the all-solid-state secondary lithium battery prepared by the Cl electrolyte and the indium cathode.
FIG. 5 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 20.85VS1.9Cl0.1An XRD pattern of (a);
FIG. 6 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 20.85VS1.9Cl0.1And lithium iron phosphate (LiFePO)4) Composite positive electrode after mixing, Li3PS4Electrolyte and Li cathode are used for preparing the full solid secondary lithium battery with the cycle performance of 0.5C at room temperature.
FIG. 7 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 30.7Zn0.1VS1.95I0.05An XRD pattern of (a);
FIG. 8 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 30.7Zn0.1VS1.95I0.05And lithium manganese iron phosphate (LiFe)0.2Mn0.8PO4) Composite positive electrode after mixing, Li7P3S11Electrolyte, room temperature multiplying power and cycle performance of the all-solid-state secondary lithium battery prepared by the Li/In alloy negative electrode.
FIG. 9 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 40.81Zn0.1Ti2(PS4)3X of (2)An RD map;
FIG. 10 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 40.81Zn0.1Ti2(PS4)3And ternary positive electrode (LiNi)0.6Mn0.2Co0.2O2) Composite positive electrode after mixing, Li6PS5I electrolyte, graphite and Li0.81Zn0.1Ti2(PS4)3The room temperature multiplying power and the cycle performance of the all-solid-state secondary lithium battery prepared by the mixed composite cathode.
FIG. 11 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 50.66Ba0.2Ti2(PS3.8Cl0.2)3An XRD pattern of (a);
FIG. 12 shows an electron-alkali metal ion mixed conduction sulfide material Li obtained in example 50.66Ba0.2Ti2(PS3.8Cl0.2)3With LiCoO2Composite positive electrode after mixing, Li10SnP2S12Electrolyte, Li4Ti5O12With Li0.66Ba0.2Ti2(PS3.8Cl0.2)3The all-solid-state secondary lithium battery prepared by the mixed composite negative electrode has the room temperature 0.5C cycle performance.
FIG. 13 shows the use of LiCoO in comparative examples2With Li6PS5Composite positive electrode after Cl mixing, Li6PS5Room temperature multiplying power and cycle performance of the all-solid-state secondary lithium battery prepared by the Cl electrolyte and the indium cathode.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
The sulfide material with both alkali metal ions and electron conduction can realize the characteristic of mixed conduction of electrons and alkali metal ions, and is applied to the sulfide-based all-solid-state battery, so as to solve the problems that the composite anode of the sulfide-based all-solid-state battery in the prior art has low electron conductivity, so that the room-temperature rate performance of the battery is poor, and the development and application of the sulfide-based all-solid-state battery are limited.
Example 1
Preparation of A-site doped AMS2Sulfide material, wherein a is Li, a' is Ba, M is Cr, y = 0, x = 0.1, z = 0.21, resulting in a material Li0.79Ba0.1CrS2。
Respectively taking Li in a protective atmosphere2S，BaS，Cr2S3And S, feeding materials according to the four molar ratios of 3.95: 1: 5: 0.05, ball-milling and uniformly mixing at the rotating speed of 200 r/min, placing the mixture in a tubular sintering furnace, introducing argon into the tube, sintering at the temperature of 750 ℃ for 10 hours, naturally cooling, collecting products, crushing and collecting to obtain Li0.79Ba0.1CrS2The crystal structure is shown in figure 1. The resulting material, as seen by the crystalline structure, has AMS2The target product is successfully obtained through the crystal form of the material.
And (3) testing the electronic conductivity and the ionic conductivity of the obtained sulfide, specifically:
method for testing electronic conductivity
The obtained material was uniformly spread in a conventional mold (see fig. 2), molded under a pressure of 8 MPa and under a certain bias (c)
Figure 835676DEST_PATH_IMAGE002
) Carrying out direct current polarization, the current after the polarization is completed is
Figure 104983DEST_PATH_IMAGE003
Then the electron conductivity of the material is
Figure 952854DEST_PATH_IMAGE004
Wherein L is the sample thickness and S is the sample base area.
Method for testing ionic conductivity
The above-obtained material, metallic Li flakes and Li were mixed in a structure shown in FIG. 3+Conductor Li6PS5Cl is assembled in a mold under a certain bias (C)
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) Carrying out direct current polarization, the current after the polarization is completed is
Figure 679556DEST_PATH_IMAGE003
Then the electron conductivity of the material is
Figure 6632DEST_PATH_IMAGE006
Wherein L is the thickness of the sample, S is the bottom area of the sample, and R is the resistance value of the alkali metal ion conductive material.
Room temperature Li of the measured Material+Conductivity of 0.35 mS cm−1Electron conductivity of 6.3S cm−1。
Preparation of all-solid-state secondary lithium battery
In a protective atmosphere, LiCoO2With Li prepared in this example0.79Ba0.1CrS2Uniformly mixing the materials according to the mass ratio of 7: 3 to obtain positive electrode powder; a disk of 9 mm in diameter was cut out of indium metal and used as a negative electrode. 80 mg of Li are weighed6PS5Placing Cl into a die with the diameter of 10 mm, and molding under the pressure of 6 MPa; weighing 10 mg of anode powder, and uniformly spreading the anode powder to Li6PS5One side of Cl is molded under the pressure of 8 MPa; finally, the indium sheet is flatly placed in Li6PS5The other side of Cl is molded under a pressure of 2 MPa to obtain LiCoO2+Li0.79Ba0.1CrS2|Li6PS5Cl | In all solid state batteries.
And (3) carrying out room-temperature electrochemical performance test on the obtained all-solid-state secondary lithium battery:
cycling at room temperature at 0.05, 0.1, 0.2, 0.4, 0.6 and 0.8C rate for 5 weeks (2.8-4.2V vs Li/Li) using a charge-discharge instrument (Wuhan LAND)+) And then long cycling at 1C magnification. As shown in fig. 4, at a lower rate (0.05C), the all-solid battery can exert 152 mAh g−1High specific capacity of (2). Along with the increase of the multiplying power, the specific discharge capacity of the battery is gradually reduced to 108 mAh g at 0.8C−1. Even at 1C magnification, allThe solid-state battery can still play a role of 101 mAh g−1High specific capacity and stable cycling for 120 weeks.
Example 2
Preparation of S-site doped AMS2Wherein a is Li, M is V, S' is Cl, x = 0, y = 0.1, z = 0.15, giving a material Li0.85VS1.9Cl0.1。
Respectively taking Li in a protective atmosphere2S，V2S3LiCl and S are added according to the four molar ratios of 3.75: 5: 1: 0.25, the mixture is ball-milled and uniformly mixed at the rotating speed of 250 r/min, then the mixture is placed in a tubular sintering furnace, argon is introduced into the tube, the mixture is sintered for 12 hours at the temperature of 650 ℃, products are collected after natural cooling, and the products are crushed and collected to obtain Li0.85VS1.9Cl0.1The crystal structure is shown in FIG. 5. The resulting material, as seen by the crystalline structure, has AMS2The target product is successfully obtained through the crystal form of the material.
The electron and ion conductivity were measured in the same manner as in example 1.
Room temperature Li of the measured Material+Conductivity of 0.63 mS cm−1Electron conductivity of 4.7S cm−1。
Preparation of all-solid-state secondary lithium battery
In a protective atmosphere, lithium iron phosphate (LiFePO)4) With Li prepared in this example0.85VS1.9Cl0.1Uniformly mixing the materials according to the mass ratio of 7: 3 to obtain positive electrode powder; the metal Li was cut into a 6 mm diameter disk and used as a negative electrode. 80 mg of Li are weighed3PS4Placing into a mold with a diameter of 10 mm, and molding under the pressure of 6 MPa; weighing 10 mg of anode powder, and uniformly spreading the anode powder to Li3PS4Molding at a pressure of 8 MPa; finally, the Li plate is flatly placed in Li3PS4At a pressure of 2 MPa to obtain LiFePO4+Li0.85VS1.9Cl0.1|Li3PS4All-solid-state battery of | Li.
Carrying out room temperature electrochemical performance test on the obtained all-solid-state secondary lithium battery
By charging and dischargingElectric instrument (Land in Wuhan) at room temperature under 0.5C rate (2.8-4.0V vs Li/Li)+) And (5) carrying out next long circulation. As shown in FIG. 6, the all-solid battery can exert 152 mAh g−1The specific capacity is high, the capacity retention rate after 100 weeks is 98.7%, and the coulombic efficiency is higher than 99%.
Example 3
Preparation of A-site and S-site co-doped AMS2Wherein a is Li, a 'is Zn, M is V, S' is I, x = 0.1, y = 0.05, z = 0.3, yielding a material Li0.7Zn0.1VS1.95I0.05。
Respectively taking Li in a protective atmosphere2S，ZnS，V2S3LiI and S are added according to the five molar ratios of 3.25: 1: 5: 0.5: 0.25, the mixture is ball-milled and mixed evenly at the rotating speed of 300 r/min, then the mixture is placed in a tubular sintering furnace, argon is introduced into a tube, the mixture is sintered for 12 hours at the temperature of 700 ℃, products are collected after natural cooling, and the products are crushed and collected to obtain Li0.7Zn0.1VS1.95I0.05The crystal structure is shown in FIG. 7. The resulting material, as seen by the crystalline structure, has AMS2The target product is successfully obtained through the crystal form of the material.
The electron and ion conductivity were measured in the same manner as in example 1.
Room temperature Li of the measured Material+Conductivity of 0.65 mS cm−1Electron conductivity of 4.4S cm−1。
Preparation of all-solid-state secondary lithium battery
In a protective atmosphere, lithium manganese iron phosphate (LiFe)0.2Mn0.8PO4) With Li prepared in this example0.7Zn0.1VS1.95I0.05Uniformly mixing the materials according to the mass ratio of 7: 3 to obtain positive electrode powder; the Li/In alloy was cut into a disk having a diameter of 8 mm and used as a negative electrode. 80 mg of Li are weighed7P3S11Placing into a mold with a diameter of 10 mm, and molding under the pressure of 6 MPa; weighing 10 mg of anode powder, and uniformly spreading the anode powder to Li7P3S11Molding at a pressure of 7 MPa; finally, the Li/In sheet is flatly placed In Li7P3S11And molding the other side of the die under the pressure of 2 MPa to obtain LiFe0.2Mn0.8PO4+Li0.7Zn0.1VS1.95I0.05|Li7P3S11An all-solid-state battery of | Li/In.
Carrying out room temperature electrochemical performance test on the obtained all-solid-state secondary lithium battery
Using a charge-discharge instrument (Land in Wuhan), at room temperature at 0.1, 0.3, 0.5 and 1C rate (2.8-4.35V vs Li/Li)+) Charge and discharge and long cycle at 0.5C rate. As shown in fig. 8, at 0.1, 0.3, 0.5, and 1C rates, the all-solid battery can exert 140, 137, 132, and 90 mAh g−1The specific capacity of (A). Then the long circulation at 0.5C still can exert 119 mAh g after 120 weeks−1The specific capacity, the capacity retention rate is 90.2%, and the coulombic efficiency is higher than 99%.
Example 4
Preparation of A-doped ATi2(PS4)3A is Li, a' is Zn, y = 0, x = 0.1, z = 0.19, giving the material Li0.81Zn0.1Ti2(PS4)3。
Respectively taking Li in a protective atmosphere2S，ZnS，TiS2Feeding P and S according to the five molar ratio of 4.05: 1: 20: 30: 74.95, ball-milling and uniformly mixing at the rotating speed of 330 r/min, placing in a tubular sintering furnace, introducing argon into a tube, sintering at 280 ℃ for 8 h, naturally cooling, collecting a product, crushing and collecting to obtain Li0.81Zn0.1Ti2(PS4)3The crystal structure is shown in FIG. 9. The resulting material, as seen by the crystalline structure, had a value of ATi2(PS4)3The target product is successfully obtained through the crystal form of the material.
The electron and ion conductivity were measured in the same manner as in example 1.
Room temperature Li of the measured Material+Conductivity of 0.19 mS cm−1Electron conductivity of 6.9S cm−1。
Preparation of all-solid-state secondary lithium battery
In a protective atmosphere, a ternary positive electrode（LiNi0.6Mn0.2Co0.2O2) With Li prepared in this example0.81Zn0.1Ti2(PS4)3Uniformly mixing the materials according to the mass ratio of 7: 3 to obtain positive electrode powder; graphite powder and Li prepared in the example0.81Zn0.1Ti2(PS4)3Uniformly mixing the components according to the mass ratio of 4: 6 to obtain the negative electrode powder. 80 mg of Li are weighed6PS5I, placing the mixture into a die with the diameter of 10 mm, and molding under the pressure of 6 MPa; weighing 10 mg of anode powder, and uniformly spreading the anode powder to Li6PS5One side of the I is molded under the pressure of 8 MPa; 30 mg of negative electrode powder is weighed and uniformly spread to Li6PS5The other side of I is molded under the pressure of 8 MPa to obtain LiNi0.6Mn0.2Co0.2O2+Li0.81Zn0.1Ti2(PS4)3|Li6PS5I|C+Li0.81Zn0.1Ti2(PS4)3An all-solid-state battery.
Carrying out room temperature electrochemical performance test on the obtained all-solid-state secondary lithium battery
Charging and discharging instrument (Land in Wuhan) at room temperature under 0.1 and 0.2C multiplying power (3.0-4.4V vs Li/Li)+) Charge and discharge and long cycle at 0.2C rate. As shown in FIG. 10, the all-solid battery can exhibit 184 mAh g at 0.1C rate in the first week−1The specific capacity of (A). At 0.2C, the specific capacity is reduced to 146 mAh g−1And a capacity retention rate of 86.3% (126 mAh g) after 100 weeks−1) Coulombic efficiency was higher than 99%.
Example 5
Preparation of A-site and S-site codoped ATi2(PS4)3Wherein a is Li, a 'is Ba, S' is Cl, x = 0.2, y = 0.2, z = 0.34, giving a material Li0.66Ba0.2Ti2(PS3.8Cl0.2)3。
Respectively taking Li in a protective atmosphere2S，BaS，Ti，P2S5LiCl and S according to a molar ratio of 0.3: 2: 20: 15:6: 36.7, ball-milling and uniformly mixing at the rotating speed of 350 r/min, putting the mixture into a tubular sintering furnace, introducing argon into the tube, sintering the mixture for 4 hours at the temperature of 450 ℃, naturally cooling, collecting the product, crushing and collecting the product to obtain Li0.66Ba0.2Ti2(PS3.8Cl0.2)3The crystal structure is shown in FIG. 11. The resulting material, as seen by the crystalline structure, had a value of ATi2(PS4)3The target product is successfully obtained through the crystal form of the material.
The electron and ion conductivity were measured in the same manner as in example 1.
Room temperature Li of the measured Material+The conductivity was 0.89 mS cm−1Electron conductivity of 5.5S cm−1。
Preparation of all-solid-state secondary lithium battery
In a protective atmosphere, LiCoO2With Li prepared in this example0.66Ba0.2Ti2(PS3.8Cl0.2)3Uniformly mixing the materials according to the mass ratio of 7: 3 to obtain positive electrode powder; mixing Li4Ti5O12With Li prepared in this example0.66Ba0.2Ti2(PS3.8Cl0.2)3Uniformly mixing the components according to the mass ratio of 4: 6 to obtain the negative electrode powder. 80 mg of Li are weighed10SnP2S12Placing into a mold with a diameter of 10 mm, and molding under the pressure of 6 MPa; weighing 10 mg of anode powder, and uniformly spreading the anode powder to Li10SnP2S12Molding at a pressure of 7 MPa; weighing 35 mg of negative electrode powder, and uniformly spreading the negative electrode powder on Li10SnP2S12Molding under a pressure of 8 MPa to obtain LiCoO2+Li0.66Ba0.2Ti2(PS3.8Cl0.2)3|Li10SnP2S12|Li4Ti5O12+Li0.66Ba0.2Ti2(PS3.8Cl0.2)3An all-solid-state battery.
Carrying out room temperature electrochemical performance test on the obtained all-solid-state secondary lithium battery
Charging and discharging instrument (Land in Wuhan) at room temperature under 0.5C multiplying power (2.8-4.2V vs Li/Li)+) And performing charge and discharge and circulation. As shown in FIG. 12, the all-solid-state battery can exert 144 mAh g in the first week−1After circulating for 100 weeks, the specific capacity is reduced to 123 mAh g−1The capacity retention rate is 85.4% after 100 weeks, and the coulombic efficiency is higher than 99.5%.
Example 6
Preparation of A-site doped AMS2Wherein a is Na, a' is Mg, M is Fe, y = 0, x = 0.2, z = 0.44, yielding material Na0.56Mg0.2FeS2。
Respectively taking Na in a protective atmosphere2Feeding S, MgS, FeS and S according to the molar ratio of 3.95: 1: 5: 0.05, ball-milling and uniformly mixing at the rotating speed of 370 r/min, placing in a tubular sintering furnace, introducing argon into the tube, sintering at 650 ℃ for 12 h, naturally cooling, collecting the product, crushing and collecting to obtain Na0.56Mg0.2FeS2。
The electron conductivity was measured in the same manner as in example 1; li plate is changed into Na plate in the test of ionic conductivity, and Li+Conductor Li6PS5Cl is changed into Na+Conductor Na3PS4Otherwise, the same procedure as in example 1 was repeated.
Room temperature Na of the measured Material+Conductivity of 0.12 mS cm−1Electron conductivity of 3.7S cm−1。
Example 7
Preparation of S-site doped ATi2(PS4)3Wherein a is K, S' is Br, x = 0, y =1/3, z = 0.3, yielding material K0.7Ti2(P
Figure 87721DEST_PATH_IMAGE007
)3。
Respectively taking K in protective atmosphere2S，TiS2P, LiBr and S are added according to the five molar ratios of 0.35: 2: 3: 1/3: 6.65, the mixture is ball-milled and evenly mixed at the rotating speed of 400 r/min and then is placed in a tubular sintering furnace, argon is introduced into a tube, and the temperature is 260 DEG CSintering for 6 h, naturally cooling, collecting the product, crushing and collecting to obtain K0.7Ti2(P
Figure 500247DEST_PATH_IMAGE007
)3。
Comparative examples
In a protective atmosphere, LiCoO2With pure Li+Conductor Li6PS5Uniformly mixing Cl according to the mass ratio of 7: 3 to obtain positive electrode powder; a disk of 9 mm in diameter was cut out of indium metal and used as a negative electrode. 80 mg of Li are weighed6PS5Placing Cl into a die with the diameter of 10 mm, and molding under the pressure of 6 MPa; weighing 10 mg of anode powder, and uniformly spreading the anode powder to Li6PS5One side of Cl is molded under the pressure of 8 MPa; finally, the indium sheet is flatly placed in Li6PS5The other side of Cl is molded under a pressure of 2 MPa to obtain LiCoO2+Li6PS5Cl|Li6PS5Cl | In all solid state batteries.
And (3) testing the room temperature multiplying power and the cycle performance of the obtained all-solid-state secondary lithium battery:
using a charge-discharge instrument (Wuhan LAND), circulating at room temperature at 0.05, 0.1, 0.2, 0.5 and 1.0C multiplying power for 10 weeks (2.8-4.2V vs Li/Li)+) And then long cycling at 0.2C magnification. As shown in fig. 13, at a lower rate (0.05C), the all-solid battery can exert 133 mAh g−1Is lower than the capacity (152 mAh g) of the all-solid-state secondary lithium battery in the example 1 under the same multiplying power−1). When the multiplying power is increased to 1.0C, the specific discharge capacity of the battery is gradually reduced to 40 mAh g−1And poor cycle performance. In contrast, the all-solid-state secondary lithium battery using the sulfide material with mixed electron and ion conduction in example 1 to prepare the composite positive electrode still had 101 mAh g−1High specific capacity and stable circulation.
It can be seen from the above examples that the sulfide materials obtained all have high Li+Electrical conductivity (10)−4～10−3 S cm−1) And electron conductivity (1-1)0 S cm−1) And further, the sulfide-based all-solid battery is assembled by mixing the sulfide-based all-solid battery with the positive electrode and/or the negative electrode, and the room-temperature rate capability of the sulfide-based all-solid battery is improved, so that the commercialization process of the sulfide-based all-solid battery is greatly promoted.
According to the invention, the sulfide material containing the alkali metal element and the transition metal element is substituted by the aliovalent element, so that the alkali metal ion concentration is regulated and controlled to improve the alkali metal ion conductivity of the sulfide material and the valence state of the transition metal element to improve the electron conductivity of the sulfide material. The sulfide material has an electron conductivity of not less than 1S cm at room temperature−1The ionic conductivity is not less than 0.1 mS cm−1. The invention also discloses an all-solid-state battery assembled by the sulfide material.

Claims (7)

1. The sulfide material with mixed conduction of electrons and alkali metal ions is characterized in that the general formula of the sulfide material is AMS2Or ATi2(PS4)3In the general formula, A-site and/or S-site aliovalent elements are doped; wherein, A site is alkali metal element, and A site aliovalent doping element is valence>+1 metal element, S-site aliovalent doping element is halogen, M is transition metal element.
2. An electron-alkali metal ion mixed conduction sulfide material as claimed in claim 1, wherein the sulfide material is doped with an aliovalent element at the A-position and/or the S-position in the formula so that the valence of M or Ti in the formula is changed and the quantity of A is changed, i.e. the formula is A1−zA'xMS2−yS'yOr A1−zA'xTi2(PS4−yS'y)3Wherein x, y and z satisfy the valence requirement of the general formula, and x and y are not 0, 0 at the same time< z < 1。
3. The electronic and alkali metal ion mixed conduction sulfide material according to any one of claims 1 to 2, wherein a is one or more of Li, Na, and K; m is one or more of Fe, Co, Ti, V and Cr; a' is one or more of Ca, Mg, Sr, Ba and Zn; s' is one or more of F, Cl, Br and I.
4. Use of the electronically and alkali metal ion mixed conducting sulfide material of claim 1 as a conductive aid.
5. An all-solid-state secondary lithium battery comprising a positive electrode, a negative electrode and an all-solid-state electrolyte between the positive electrode and the negative electrode, wherein the positive electrode or/and the negative electrode comprises the electronic and alkali metal ion mixed conductive sulfide material according to claim 1.
6. An all-solid-state lithium secondary battery as claimed in claim 5, wherein: the positive electrode also comprises a positive electrode active material, wherein the positive electrode active material is lithium cobaltate, lithium iron phosphate, lithium manganese oxide, lithium nickel manganese oxide, a ternary material, ferric phosphate salt or ferric manganese phosphate salt, and the all-solid-state electrolyte material is 80Li2S : 20P2S5；Li9+x-yMxP3-xS12-yXyWherein X is more than or equal to 0 and less than or equal to 2, M is one or more of Si, Ge, Sn and Pb, y is more than or equal to 0 and less than or equal to 1, and X is one or more of F, Cl, Br and I; li6PS5X and X are one or more of F, Cl, Br and I; 75Li2S : 25P2S5；Li3PS4；70Li2S : 30P2S5And Li7P3P11One or more of the above; the negative electrode also comprises a negative electrode active material, wherein the negative electrode active material is a metal lithium sheet, a metal lithium alloy, a metal indium sheet, graphite, hard carbon, lithium titanate, graphene or silicon carbon negative electrode.
7. A method for preparing the all-solid-state secondary lithium battery as claimed in claim 5, wherein the positive electrode, the all-solid-state electrolyte and the negative electrode are laminated in sequence to form an integrated all-solid-state secondary lithium battery with a sandwich structure.
CN202110742401.4A 2021-07-01 2021-07-01 Sulfide material with mixed conduction of electrons and alkali metal ions and application thereof Pending CN113690434A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114447281A (en) * 2022-01-29 2022-05-06 天目湖先进储能技术研究院有限公司 TiS2Composite positive electrode and all-solid-state battery device
CN114497712A (en) * 2022-01-26 2022-05-13 浙江锋锂新能源科技有限公司 Electron-ion mixed conductor electrolyte, preparation method thereof and all-solid-state battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114497712A (en) * 2022-01-26 2022-05-13 浙江锋锂新能源科技有限公司 Electron-ion mixed conductor electrolyte, preparation method thereof and all-solid-state battery
CN114447281A (en) * 2022-01-29 2022-05-06 天目湖先进储能技术研究院有限公司 TiS2Composite positive electrode and all-solid-state battery device
CN114447281B (en) * 2022-01-29 2023-06-23 天目湖先进储能技术研究院有限公司 TiS (titanium sulfide) 2 Composite positive electrode and all-solid-state battery device

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