CN108630914A - Lithium cell cathode with different sulfide type lithium ion conductors - Google Patents

Lithium cell cathode with different sulfide type lithium ion conductors Download PDF

Info

Publication number
CN108630914A
CN108630914A CN201810234813.5A CN201810234813A CN108630914A CN 108630914 A CN108630914 A CN 108630914A CN 201810234813 A CN201810234813 A CN 201810234813A CN 108630914 A CN108630914 A CN 108630914A
Authority
CN
China
Prior art keywords
cathode
lithium ion
ion conductor
type lithium
sulfide type
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810234813.5A
Other languages
Chinese (zh)
Inventor
I.克卡姆
力矢.吉田
T.胡普费尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of CN108630914A publication Critical patent/CN108630914A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • H01M2004/028—Positive 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to the lithium cell cathodes with different sulfide type lithium ion conductors.Include active material of cathode particle 11 the present invention relates to the cathode 10,10 for lithium battery 1.In order to be provided in a manner of cost advantages with improved cyclical stability and the lithium battery of calendar storage time 1, active material of cathode particle 11 is at least coated with the first sulfide type lithium ion conductor 12, wherein coated active material of cathode particle 11,12 is embedded in the second sulfide type lithium ion conductor 13 different from the first sulfide type lithium ion conductor, and 13 be binary sulfide type lithium ion conductor.In addition, the present invention relates to its manufacturing method and corresponding lithium batteries 1.

Description

Lithium cell cathode with different sulfide type lithium ion conductors
Technical field
The present invention relates to cathode, its manufacturing method and the corresponding lithium batteries for lithium battery.
Background technology
Lithium ion battery and-battery pack based on solid can have for example>The high energy density of 400 Wh/kg With --- such as caused by cancelling liquid electrolyte --- extraordinary security performance.
2014/0287324 A1 of printed document US describe active material of cathode particle, with by sulfide type solid electricity Solve coating coating made of matter.
2014/0057180 A1 of printed document US describe oxide type active material, with including oxide type solid The coating of electrolyte and conductive agent coats.Here, coated oxide type active material connects with sulfide type solid electrolyte It touches.
Invention content
Subject of the present invention is the cathode for lithium battery, and it includes active material of cathode particle, the active material of cathode Particle is at least coated by the first sulfide type lithium ion conductor.Here, coated active material of cathode particle is particularly embedded in In the second especially different from the first sulfide type lithium ion conductor sulfide type lithium ion conductors.Here, second sulfide Type lithium ion conductor especially binary sulfide type lithium ion conductor.
Binary sulfide type lithium ion conductor can particularly be understood to mean following sulfide type lithium ion conductor, By the sulfide of two kinds of different elements, especially formed by lithium and the other elements different from lithium, such as the sulfide of phosphorus.Binary The example of sulfide type lithium ion conductor is glassy and/or ceramic Li2S/P2S5, such as glassy Li2S/P2S5And/or glass Shape-ceramics Li2S/P2S5, especially there is crystallised component, such as in Li7P3S11Form.
Sulfide type lithium ion conductor can advantageously have very high lithium ion conductivity.By by the cathode activity Material granule is coated with the first sulfide type lithium ion conductor and is embedded in coated active material of cathode particle and first In the second different sulfide type lithium ion conductor of sulfide type lithium ion conductor, both sulfide type lithium ions can be led Body optimizes towards their own application and improves the lithium ion conductive between active material of cathode.Pass through the second vulcanization Object type lithium ion conductor is binary sulfide type lithium ion conductor, it can be advantageous to be realized in a manner of simple and cost advantages Sufficiently high lithium ion conductive between grain.First sulfide type lithium ion conductor can herein advantageously live to cathode at it Property material chemical stability in terms of optimally select.Active material of cathode particle and the second sulfide can be optimized by this method Therefore interface stability between type lithium ion conductor simultaneously advantageously improves cyclical stability and calendar storage time （kalendarische Speicherdauer）.
Generally, it can therefore advantageously be provided in a manner of cost advantages and be deposited with improved cyclical stability and calendar Store up the lithium battery of time.
In one embodiment, the second sulfide type lithium ion conductor is glassy and/or ceramic binary sulfide Type lithium ion conductor, is based particularly on Li2S/P2S5。
For example, the second sulfide type lithium ion conductor can include or vitreous amorphous Li2S/P2S5, such as With 70/30 to 80/20 ratio, such as at room temperature 10-4To 10-3 The lithium ion conductivity of S/cm；And/or comprising Or the Li of glassy-ceramics2S/P2S5, with crystallised component, such as in Li7P3S11Form, such as at room temperature 10-3To 10-2 The lithium ion conductivity of S/cm.
In another embodiment, the active material of cathode particle includes oxide type active material of cathode, such as Nickel, cobalt and manganese oxide and/or nickel cobalt aluminum oxide especially have for example>The high nickel content of 33 moles of %, such as NCM622 And/or NCM811 and/or NCA；Or it is formed by it.Therefore, it can be advantageous to realize high energy density.
In another embodiment, the first sulfide type lithium ion conductor is the sulfide type lithium of binary or at least ternary Ion conductor.
At least the sulfide type lithium ion conductor of ternary can particularly be understood to mean following sulfide type lithium ion Conductor, by the sulfide of three or more different elements, especially by the other elements different from lithium of lithium and at least two Sulfide formed.
For example, the first sulfide type lithium ion conductor can include or binary sulfide type lithium ion conductor, such as glass The amorphous Li of glass shape2S/P2S5, such as with >=70/30 to≤80/20 ratio, such as at room temperature 10-4Extremely 10-3The lithium ion conductivity of S/cm；And/or the Li of glassy-ceramics2S/P2S5, with crystallised component, such as in Li7P3S11Form, such as at room temperature 10-3To 102The lithium ion conductivity of S/cm；And/or comprising or at least three The sulfide type lithium ion conductor of member, such as with space group P 42/ nmc, such as Li10GeP2S12、Li10SnP2S12、 Li9.54Si1.74P1.44S11.7Cl0.3And/or Li9.6P3S12, such as at room temperature 10-3To 10-2 The lithium ion conductance of S/cm Rate；And/or lithium-argyrodite, such as Li7PS6、Li6PS5Cl、Li6PS5I and/or Li6PS5Br, such as with space group F- 43 m, such as at room temperature 10-3To 10-2 Lithium ion conductivity.
In another embodiment, the first sulfide type lithium ion conductor is lithium-argyrodite.
Lithium-argyrodite can be particularly understood to mean derived from chemical general formula Ag8GeS6Mineral argyrodites Compound, wherein silver-colored (Ag) is substituted by lithium (Li), and wherein can in particular, germanium (Ge) partially or completely and/or sulphur (S) partly by other elements, such as the element substitution of Section III, IV, V, VI and/or VII main group.
Lithium-argyrodite can such as have advantageously with to the oxide type active material of cathode with high-energy density There are the oxide type active material of cathode of high nickel content, such as the high chemical stability of NCM622 and/or NCM811 and/or NCA.
For example, the first sulfide type lithium ion conductor can include or
Lithium-argyrodite of following chemical formula：
Li7PS6
And/or
Lithium-argyrodite of at least one following chemical general formula：
Li6PS5X
Wherein X indicates chlorine (Cl) and/or bromine (Br) and/or iodine (I) and/or fluorine (F),
Such as X indicates chlorine (Cl) and/or bromine (Br) and/or iodine (I),
And/or
Lithium-argyrodite of at least one following chemical general formula：
Li7-δBS6-δXδ
Wherein B indicates that phosphorus (P) and/or arsenic (As), X indicate chlorine (Cl) and/or bromine (Br) and/or iodine (I) and/or fluorine (F), such as X indicates chlorine (Cl) and/or bromine (Br) and/or iodine (I), and 0≤δ≤1.
For example, the first sulfide type lithium ion conductor can include or lithium-argyrodite of following chemical formula：Li7PS6、 Li6PS5Cl、Li6PS5Br、Li6PS5I、Li7-δPS6-δClδ、Li7-δPS6-δBrδAnd/or Li7-δPS6-δIδ。
In one embodiment, the first sulfide type lithium ion conductor is at least ternary, especially ternary or quaternary Or the sulfide type lithium ion conductor comprising more kinds of elements.Ternary and more advanced sulfide type lithium ion conductor, such as three Member or quaternary or sulfide type lithium ion conductor comprising more kinds of elements can advantageously have extra high for having height The oxide type active material of cathode of energy density, such as the oxide type active material of cathode with high nickel content, such as The chemical stability of NCM622 and/or NCM811 and/or NCA.
In another embodiment, the first sulfide type lithium ion conductor is lithium-argyrodite and/or lithium-phosphorus-vulcanization Object, it includes at least one halide, especially chloride and/or iodide and/or bromide and/or germanium and/or tin and/ Or silicon.This lithium ion conductor can advantageously have low contact resistance（Übergangswiderstand）With it is extra high For the oxide type active material of cathode with high-energy density, such as the oxide type cathode active material with high nickel content Material, for example, NCM622 and/or NCM811 and/or NCA chemical stability.
In another embodiment, the active material of cathode particle is further with made of other lithium ion conductors Intervening layers.Here, middle layer is coated with the coating made of the first sulfide type lithium ion conductor again.By among this Layer, can reduce the contact resistance between active material of cathode and the first sulfide type lithium ion conductor.
In an embodiment of the embodiment, other lithium ion conductors of the middle layer include or boric acid Lithium, especially Li3BO3And/or LiBO2And/or lithium sulfate, such as Li2SO4And/or tungstate lithium, such as Li2WO4And/or molybdenum Sour lithium, such as Li2MoO4.This lithium ion conductor is proved to be particularly advantageous for reducing contact resistance.
The cathode can be further equipped with cathode current collector（Stromleiter）.
In another embodiment, the cathode is manufactured by the method being described below.
With binary or at least ternary sulfide type lithium ion conductor coating active material of cathode particle can for example by means of Help scanning electron microscope（REM）（English：Scanning electron microscope,（SEM））, especially by element Distribution is by energy dispersion X-ray spectrum（EDX）Detection.
It is clear refering to about the method for the present invention and Ben Fa to this for the other technical characteristics and advantage of cathode of the present invention The elaboration of bright lithium battery and refering to attached drawing and description of the drawings.
Another theme of the present invention is manufacture cathode, the method for cathode especially of the present invention, wherein in following method steps In：
A) by active material of cathode particle use in binary or at least the sulfide type lithium ion conductor form of ternary first vulcanization Object type lithium ion conductor is for example coated by wet-chemical mode and/or by vapor deposition, and
B) by coated active material of cathode particle and especially different from the first sulfide type lithium ion conductor in binary Second sulfide type lithium ion conductor of sulfide type lithium ion conductor form mixes, and is for example processed into cathode.
It can for example be carried out by physical vapour deposition (PVD) and/or atomic layer deposition by the coating of vapor deposition.
In one embodiment, active material of cathode particle is led with by other lithium ions first in method and step a) Intervening layers made of body, then by the active material of cathode particle through the intervening layers with the first sulfide type lithium from Sub- conductor coating.
First sulfide type lithium ion conductor, the second sulfide type lithium ion conductor and other lithium ion conductors can be special Ground is arranged as being illustrated about cathode of the present invention.
It, can such as coated cathode collector and/or diaphragm by the mixing of method and step b).
It is clear refering to about cathode of the present invention and lithium of the present invention to this with regard to other technical characteristics and advantage of the method for the present invention The elaboration of battery and refering to attached drawing and description of the drawings.
In addition, the present invention relates to lithium batteries comprising cathode, anode and the diaphragm being arranged between the cathode and anode, Wherein the cathode is the cathode of the present invention and/or can manufacture by the method for the invention.
In one embodiment, the anode is lithium anodes.
Lithium anodes can particularly be understood to mean the anode formed comprising lithium metal or by it.
By using lithium anodes, it can be advantageous to realize high energy density.
For example, the lithium anodes can by lithium metal or lithium alloy, such as lithium magnesium alloy --- such as foil, such as lithium foil, Or coating, such as the form of lithium coating --- for example formed in the metallic substrates of such as copper and/or nickel.
In another embodiment, the diaphragm is solid electrolyte diaphragm.
For example, the diaphragm can include the sulfide type lithium ion conductor and/or oxide type lithium of binary or at least ternary Ion conductor（It is for example with garnet structure）And/or polymer dielectric, such as based on polyethylene oxide（PEO）, such as Polymer dielectric in the form of block copolymer, or formed by it.
In one embodiment, which includes the sulfide type lithium ion conductor of binary or at least ternary, such as lithium- Argyrodite and/or lithium-phosphorus-sulfide, or formed by it.
For example, the diaphragm can include following substance or be formed by it：
Lithium-argyrodite of following chemical formula：
Li7PS6
And/or
Lithium-argyrodite of at least one following chemical general formula：
Li6PS5X
Wherein X indicates chlorine（Cl）And/or bromine（Br）And/or iodine（I）And/or fluorine（F）,
Such as X indicates chlorine（Cl）And/or bromine（Br）And/or iodine（I）,
And/or
Lithium-argyrodite of at least one following chemical general formula：
Li7-δBS6-δXδ
Wherein B indicates phosphorus（P）And/or arsenic（As）, X expression chlorine（Cl）And/or bromine（Br）And/or iodine（I）And/or fluorine（F）, such as X indicates chlorine（Cl）And/or bromine（Br）And/or iodine（I）, and 0≤δ≤1.
For example, the diaphragm can include or lithium-argyrodite of following chemical formula：Li7PS6、Li6PS5Cl、 Li6PS5Br、Li6PS5I、Li7-δPS6-δClδ、Li7-δPS6-δBrδAnd/or Li7-δPS6-δIδ。
Particularly, which can include at least ternary, especially ternary or quaternary or to include the vulcanizations of more kinds of elements Object type lithium ion conductor is formed by it.
For example, the diaphragm can include lithium-argyrodite and/or lithium-phosphorus-sulfide, such as contain at least one halogenation Object, especially chloride and/or iodide and/or bromide and/or germanium and/or that of tin and/or silicon, or formed by it.
This lithium ion conductor can be advantageously with extra high for the oxide type cathode with high-energy density Active material, such as with high nickel content oxide type active material of cathode, such as NCM622 and/or NCM811 and/or NCA with And the chemical stability for lithium.
In another replacement or additional embodiment, which includes polymer dielectric, such as based on polycyclic oxygen Ethane（PEO）, for example with those of block copolymer, such as ethylene oxide-polystrene-block copolymer form, or by it It is formed.
In addition, the cathode can be equipped with anode collector equipped with cathode current collector and/or the anode.
It is clear refering to about cathode of the present invention and the present invention to this with regard to the other technical characteristics and advantage of lithium battery of the present invention Method（Lithium-Zelle）Elaboration and refering to attached drawing and description of the drawings.
Description of the drawings
The further advantage and Advantageous embodiments of present subject matter are illustrated by attached drawing and are illustrated in the following description. It should be noted here that attached drawing only has descriptive nature and is not intended to limits the present invention with any form.
Fig. 1 illustrates the schematic cross-sectional of an embodiment by the lithium battery of the present invention with cathode of the present invention, And
Fig. 2 illustrates the schematic cross-sectional of a particular embodiment by coated active material of cathode particle.
Specific implementation mode
Fig. 1, which illustrates lithium battery 1, has cathode 10, anode 20 and the diaphragm 30 being arranged between cathode 10 and anode 20.
It is coated with the first sulfide type lithium ion conductor 12 here, cathode 10 includes active material of cathode particle 11,11. Coated active material of cathode particle 11,12 is embedded herein to be especially second different from the first sulfide type lithium ion conductor In sulfide type lithium ion conductor 13,13 be binary sulfide type lithium ion conductor, is based particularly on Li2S/P2S5Those of. First sulfide type lithium ion conductor 12 is the sulfide type lithium ion conductor of binary or at least ternary, such as lithium-sulphur silver herein Germanium mine and/or lithium-phosphorus-sulfide, further include at least one halide, such as chloride and/or iodide and/or bromine Compound and/or germanium and/or tin and/or silicon.Active material of cathode particle 11 can be particularly by oxide type cathode active material Material, such as nickel, cobalt and manganese oxide and/or nickel cobalt aluminum oxide --- it especially has high nickel content --- such as NCM622 and/ Or NCM811 and/or NCA are formed.
Anode 20 is especially lithium anodes, such as is made of lithium metal or lithium alloy.
Diaphragm 30 is solid electrolyte diaphragm, for example, by binary or at least the sulfide type lithium ion conductor of ternary and/ Or oxide type lithium ion conductor and/or polymer dielectric, such as based on ethylene oxide（PEO）, such as block copolymer shape Those of formula is made.
Fig. 1 is further illustrated, and cathode 10 is equipped with cathode current collector 40, and anode 20 is equipped with anode collector 50.
Fig. 2 is illustrated, and in one particular embodiment, active material of cathode particle 11 can be further with by other lithiums Ion conductor 12', such as Li3BO3、LiBO2、Li2SO4、Li2WO4And/or Li2MoO4Manufactured middle layer 12' coatings, wherein in Then interbed 12' is coated with the coating 12 made of the first sulfide type lithium ion conductor 12 again.

Claims (15)

1. the cathode (10) for lithium battery (1) comprising
Active material of cathode particle (11), (11) are at least coated with the first sulfide type lithium ion conductor (12), wherein through applying The embedded second sulfide type lithium different from the first sulfide type lithium ion conductor of the active material of cathode particle (11,12) that covers from In sub- conductor (13), wherein the second sulfide type lithium ion conductor (13) is binary sulfide type lithium ion conductor.
2. cathode (10) according to claim 1, wherein the second sulfide type lithium ion conductor (13) is to be based on Li2S/P2S5's Glassy and/or ceramic binary sulfide type lithium ion conductor.
3. according to the cathode (10) of claims 1 or 2, wherein the first sulfide type lithium ion conductor (12) is binary or at least three The sulfide type lithium ion conductor (12) of member.
4. according to the cathode (10) of any one of claims 1 to 3, wherein the first sulfide type lithium ion conductor (12) is lithium-sulphur Silver-colored germanium mine and/or lithium-phosphorus-sulfide, especially include at least one halide, especially chloride and/or iodide and/or Bromide and/or germanium and/or that of tin and/or silicon.
5. according to the cathode (10) of any one of Claims 1-4, wherein the first sulfide type lithium ion conductor (12) is at least three Member, especially ternary or quaternary or sulfide type lithium ion conductor comprising more kinds of elements.
6. according to the cathode (10) of any one of claim 1 to 5, wherein active material of cathode particle (11) also with by other lithiums from Middle layer (12') made of sub- conductor (12') coats, wherein middle layer (12') and with by the first sulfide type lithium ion conductor (12) coating made of (12) coats.
7. according to the cathode (10) of any one of claim 1 to 6, wherein other lithium ion conductors (12') of middle layer (12') wrap Boronic acid containing lithium, especially Li3BO3And/or LiBO2And/or lithium sulfate, especially Li2SO4And/or tungstate lithium, especially Li2WO4And/or lithium molybdate, especially Li2MoO4。
8. cathode (10) according to any one of claims 1 to 7, wherein active material of cathode particle (11) aoxidize comprising nickel cobalt manganese Object and/or nickel cobalt aluminum oxide.
9. according to the cathode (10) of any one of claim 1 to 8, wherein cathode (10) passes through method system according to claim 10 It makes.
10. cathode (10) is manufactured, in particular according to the method for the cathode (10) of any one of claim 1 to 9, wherein in following side In method step：
A) by active material of cathode particle (11) in binary or at least sulfide type lithium ion conductor (12) form of ternary First sulfide type lithium ion conductor (12) is coated, especially by wet-chemical mode and/or by vapor deposition, and
B) by coated active material of cathode particle (11) with different from the first sulfide type lithium ion conductor be in binary sulphur The second sulfide type lithium ion conductor (13) of compound type lithium ion conductor (13) form mixes.
11. the method for manufacture cathode (10) according to claim 10, wherein by active material of cathode in method and step a) Grain (11) is coated with the middle layer (12') made of other lithium ion conductors (12') first, and then will be through middle layer The first sulfide type lithium ion conductor (12) coating of the active material of cathode particle (11,12') of (12') coating.
12. lithium battery (1) comprising cathode (10), anode (20) and the diaphragm being arranged between cathode (10) and anode (20) (30), wherein cathode (10) is according to any one of claim 1 to 9 and/or by the method according to claim 10 or 11 The cathode (10) of manufacture.
13. lithium battery (1) according to claim 12, Anodic (20) is lithium anodes.
14. according to the lithium battery (1) of claim 12 or 13, wherein the diaphragm (30) is solid electrolyte diaphragm.
15. according to the lithium battery (1) of any one of claim 12 to 14, septation (30) includes the sulphur of binary or at least ternary Compound type lithium ion conductor and/or oxide type lithium ion conductor and/or polymer dielectric.
CN201810234813.5A 2017-03-22 2018-03-21 Lithium cell cathode with different sulfide type lithium ion conductors Pending CN108630914A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017204852.2A DE102017204852A1 (en) 2017-03-22 2017-03-22 Lithium-cell cathode with different sulfide lithium-ion conductors
DE102017204852.2 2017-03-22

Publications (1)

Publication Number Publication Date
CN108630914A true CN108630914A (en) 2018-10-09

Family

ID=63450069

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810234813.5A Pending CN108630914A (en) 2017-03-22 2018-03-21 Lithium cell cathode with different sulfide type lithium ion conductors

Country Status (4)

Country Link
KR (1) KR102641025B1 (en)
CN (1) CN108630914A (en)
DE (1) DE102017204852A1 (en)
FR (1) FR3064402B1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112777625A (en) * 2019-11-01 2021-05-11 三星Sdi株式会社 Compound, solid electrolyte, electrochemical cell, method for producing compound, and protected positive electrode active material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220041356A (en) * 2020-09-25 2022-04-01 주식회사 엘지화학 Positive electrode active material coated with lithium molybdenum compound for lithium secondary battery and method for manufacturing the same

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011187370A (en) * 2010-03-10 2011-09-22 Toyota Motor Corp All solid battery
CN103339768A (en) * 2011-02-04 2013-10-02 丰田自动车株式会社 Coated active material, battery, and method for producing coated active material
CN103534845A (en) * 2011-05-26 2014-01-22 丰田自动车株式会社 Coated active material, and lithium solid-state battery
CN103548186A (en) * 2011-05-23 2014-01-29 丰田自动车株式会社 Positive electrode active material particles, and positive electrode and all-solid-state battery using same
US20140057180A1 (en) * 2011-05-13 2014-02-27 Toyota Jidosha Kabushiki Kaisha Electrode body, all solid state battery, and method for producing coated active material
CN103633329A (en) * 2012-08-28 2014-03-12 华为技术有限公司 All-solid state lithium ion battery composite positive electrode material and preparation method thereof, and all-solid state lithium ion battery
US20140287324A1 (en) * 2011-11-17 2014-09-25 Toyota Jidosha Kabushiki Kaisha Electrolyte-coated cathode active material particles, all solid state battery, and method for producing electrolyte-coated cathode active material particles
CN105556730A (en) * 2013-09-27 2016-05-04 罗伯特·博世有限公司 Method of producing a lithium cell functional layer
CN105830260A (en) * 2013-11-29 2016-08-03 汉阳大学校产学协力团 Active material for all-solid lithium secondary battery, method for manufacturing same, and all-solid lithium secondary battery comprising same
WO2017033480A1 (en) * 2015-08-26 2017-03-02 株式会社日立製作所 All-solid-state lithium secondary battery and secondary battery system provided with said secondary battery

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5725054B2 (en) * 2013-02-08 2015-05-27 トヨタ自動車株式会社 Composite active material and method for producing the same
JP6222134B2 (en) * 2015-02-25 2017-11-01 トヨタ自動車株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011187370A (en) * 2010-03-10 2011-09-22 Toyota Motor Corp All solid battery
CN103339768A (en) * 2011-02-04 2013-10-02 丰田自动车株式会社 Coated active material, battery, and method for producing coated active material
US20140057180A1 (en) * 2011-05-13 2014-02-27 Toyota Jidosha Kabushiki Kaisha Electrode body, all solid state battery, and method for producing coated active material
CN103548186A (en) * 2011-05-23 2014-01-29 丰田自动车株式会社 Positive electrode active material particles, and positive electrode and all-solid-state battery using same
CN103534845A (en) * 2011-05-26 2014-01-22 丰田自动车株式会社 Coated active material, and lithium solid-state battery
US20140287324A1 (en) * 2011-11-17 2014-09-25 Toyota Jidosha Kabushiki Kaisha Electrolyte-coated cathode active material particles, all solid state battery, and method for producing electrolyte-coated cathode active material particles
CN103633329A (en) * 2012-08-28 2014-03-12 华为技术有限公司 All-solid state lithium ion battery composite positive electrode material and preparation method thereof, and all-solid state lithium ion battery
CN105556730A (en) * 2013-09-27 2016-05-04 罗伯特·博世有限公司 Method of producing a lithium cell functional layer
CN105830260A (en) * 2013-11-29 2016-08-03 汉阳大学校产学协力团 Active material for all-solid lithium secondary battery, method for manufacturing same, and all-solid lithium secondary battery comprising same
WO2017033480A1 (en) * 2015-08-26 2017-03-02 株式会社日立製作所 All-solid-state lithium secondary battery and secondary battery system provided with said secondary battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112777625A (en) * 2019-11-01 2021-05-11 三星Sdi株式会社 Compound, solid electrolyte, electrochemical cell, method for producing compound, and protected positive electrode active material

Also Published As

Publication number Publication date
KR102641025B1 (en) 2024-02-28
FR3064402B1 (en) 2022-10-28
KR20180107726A (en) 2018-10-02
DE102017204852A1 (en) 2018-09-27
FR3064402A1 (en) 2018-09-28

Similar Documents

Publication Publication Date Title
Li et al. ZnSe modified zinc metal anodes: toward enhanced zincophilicity and ionic diffusion
Liu et al. Coupling a sponge metal fibers skeleton with in situ surface engineering to achieve advanced electrodes for flexible lithium–sulfur batteries
He et al. 3D CoSe@ C aerogel as a host for dendrite‐free lithium‐metal anode and efficient sulfur cathode in Li–S full cells
Zhang et al. Emerging nonaqueous aluminum‐ion batteries: challenges, status, and perspectives
Lu et al. Carbon materials for stable Li metal anodes: Challenges, solutions, and outlook
Cheng et al. Li metal anode in working lithium-sulfur batteries
Zhang et al. Tailored yolk–shell Sn@ C nanoboxes for high‐performance lithium storage
Yang et al. Silicon-nanoparticle-based composites for advanced lithium-ion battery anodes
Xiong et al. Galvanically replaced artificial interfacial layer for highly reversible zinc metal anodes
US7521153B2 (en) Corrosion protection using protected electron collector
Wang et al. Improving the interfacial stability between lithium and solid‐state electrolyte via dipole‐structured lithium layer deposited on graphene oxide
Choi et al. In Situ Formed Ag‐Li Intermetallic Layer for Stable Cycling of All‐Solid‐State Lithium Batteries
JP2016534493A (en) ELECTRODE MATERIAL HAVING LITHIUM-ALDIRODITE
Yu et al. Ambient‐Temperature Energy Storage with Polyvalent Metal–Sulfur Chemistry
Yu et al. Insight on the Double‐Edged Sword Role of Water Molecules in the Anode of Aqueous Zinc‐Ion Batteries
EP3376581B1 (en) Solid electrolyte and secondary battery
US20170324113A1 (en) Metal sulfide anolytes for electrochemical cells
Kong et al. Ultrathin HfO2-modified carbon nanotube films as efficient polysulfide barriers for Li-S batteries
Lin et al. Challenge and strategies in room temperature sodium–sulfur batteries: A comparison with lithium–sulfur batteries
Yan et al. Controllable CN site assisting observable potential difference for homogeneous copper deposition in aqueous Cu-S batteries
Blázquez et al. A practical perspective on the potential of rechargeable Mg batteries
Zhang et al. Regulating Li uniform deposition by lithiophilic interlayer as Li-ion redistributor for highly stable lithium metal batteries
Hu et al. Two‐dimensional material‐functionalized separators for high‐energy‐density metal–sulfur and metal‐based batteries
Ren et al. CoP nanocages intercalated MXene nanosheets as a bifunctional mediator for suppressing polysulfide shuttling and dendritic growth in lithium-sulfur batteries
CN112928277A (en) Anode-free all-solid-state battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20181009