CN113853697A - Solid-state battery - Google Patents

Solid-state battery Download PDF

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Publication number
CN113853697A
CN113853697A CN201980087550.2A CN201980087550A CN113853697A CN 113853697 A CN113853697 A CN 113853697A CN 201980087550 A CN201980087550 A CN 201980087550A CN 113853697 A CN113853697 A CN 113853697A
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CN
China
Prior art keywords
battery according
electrolyte
film
battery
negative electrode
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Pending
Application number
CN201980087550.2A
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Chinese (zh)
Inventor
帕斯夸莱·福特
埃里克·克普
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.)
S2 Battery Co ltd
Eldor Corporation SpA
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S2 Battery Co ltd
Eldor Corporation SpA
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Filing date
Publication date
Application filed by S2 Battery Co ltd, Eldor Corporation SpA filed Critical S2 Battery Co ltd
Publication of CN113853697A publication Critical patent/CN113853697A/en
Pending legal-status Critical Current

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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
    • H01M4/13—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
    • 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
    • H01M10/056—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2300/0071—Oxides
    • 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

Abstract

A solid-state battery includes a positive electrode (2), a negative electrode (3), and an electrolyte (4) disposed between the positive electrode (2) and the negative electrode (3). At least one of the positive electrode (2), the negative electrode (2) or the electrolyte (4) is defined by a thin film made of a ceramic material exhibiting high ionic conductivity. The film is monolithic and has a carbon content ranging from 0.1 to 10 atomic percent. Thin amorphous materials can alternatively be used to form substrates for various devices such as fuel cells, sensors, and membranes.

Description

Solid-state battery
Technical Field
The invention relates to a thin ceramic membrane, preferably for use in solid-state batteries (solid-state batteries), more preferably in lithium-ion solid-state batteries.
The invention has its primary application in the automotive industry, but may also be associated with other fields in general.
In fact, thin ceramic membranes have many important commercial applications, such as, for example, barrier coatings in corrosion or heat resistant applications, or even as electrolytes for electrochemical devices.
Background
With reference to the technical field of greatest importance for the purposes of the present invention, batteries in the automotive industry generally consist of a positive electrode and a negative electrode separated by an ionically conductive but electrically insulating electrolyte.
It is well known that batteries can be of the "primary" or "secondary" type, depending on whether they can be recharged, i.e. according to the type of chemical reaction which becomes the basis of ionic movement and must be reversible in the case of secondary batteries.
The secondary battery that is the focus of the present invention is available in various types and sizes, but is generally defined by mobile ions. Therefore, secondary lithium batteries are generally based on the conduction of mobile lithium ions.
The electrolyte disposed between the two electrodes can be of the liquid or solid type.
So-called "thin films", which are generally of amorphous type, are commonly used as solid electrolytes, because the edges of the grains tend to impede the movement of lithium ions within the electrolyte.
Indeed, given that lithium is transported in solid ion conductors by interstitial methods, amorphous or nanocrystalline materials exhibit consistently higher ionic conductivities than their crystalline counterparts.
Therefore, the development and use of thin films has recently become increasingly important, which has led to the production of thin films of various thicknesses (from a few nanometers to a few micrometers) and composed of various materials.
Disadvantageously, however, the films on the market today or otherwise present in research in the industry have significant drawbacks, above all high production costs.
In fact, the thin films currently on the market or otherwise present in research in the industry require long deposition times and very high production costs. For this reason, although solid-state batteries have shown remarkable properties in the aerospace and defense industries, they have so far been used only rarely in the microelectronics and automotive industries, which are significantly more important from an economic point of view in terms of quantity.
Disclosure of Invention
It is therefore an object of the present invention to provide a thin ceramic membrane and a solid-state battery that overcome the above-mentioned disadvantages of the prior art.
In particular, it is an object of the present invention to make available thin ceramic membranes and high-performance solid-state batteries which are at the same time economically producible.
The object is achieved by a solid-state battery exhibiting the characteristics of one or more of the appended claims 1 to 17.
In particular, the battery includes a positive electrode, a negative electrode, and an electrolyte disposed between the electrodes.
According to one aspect of the present invention, at least one of the positive electrode (cathode), the negative electrode (anode) or the electrolyte is defined by a thin film made of an amorphous inorganic material exhibiting high ionic conductivity and electrical isolation.
According to an additional aspect of the present invention, which is an alternative or a supplement to the preceding aspect, the thin film of inorganic amorphous material contains an alkali metal, a metalloid (metalloid) or a glass-forming nonmetal (non-metal forming the glass) and an anionic species.
The alkali metal is preferably lithium or sodium.
The metalloid or metalloid is preferably an element from group 13, 14, 15 or 16 of the periodic table.
The anionic species is preferably a chalcogen (chalcogen) or from the nitrogen group.
The ionic species is preferably oxygen.
The film preferably has a carbon content ranging from 0.1 to 10 atomic percent.
More preferably, the carbon content is lower than 2% in atomic percentage, i.e. ranges from 0.1% to 2% in atomic percentage.
It should be noted that the carbon particles within the membrane are preferably uniformly distributed such that the ceramic membrane is monolithic (monolithic, monolithic type).
In other words, by inspecting the film by means of a suitable analytical technique, it is not possible to identify regions of distinctly different carbon concentration, except, of course, for small variations which are completely random.
The film analysis technique can be, for example, X-ray photoelectron spectroscopy (XPS) or Secondary Ion Mass Spectroscopy (SIMS), and can analyze the chemical composition of a material in detail because it can analyze the stoichiometry and crystallography of a thin film.
Drawings
These and other features and their advantages will be more apparent from the following illustrative and therefore non-limiting description of a preferred and therefore non-limiting embodiment of the thin ceramic membrane and solid-state battery shown in fig. 1, which schematically shows the composition of a solid-state battery according to the invention.
Detailed Description
Referring to the drawings, numeral 1 denotes a solid-state battery according to the present invention.
The battery 1 is preferably a secondary (i.e., rechargeable) lithium ion (or lithium) battery. More preferably, the battery 1 is of an intercalated type.
An intercalation battery is a special type of secondary lithium battery in which both the anode (anode) and the cathode (cathode) are composed of intercalation compounds, which in the case of lithium batteries are defined by impregnated or intercalated elemental lithium, rather than being applied directly.
The structure of the battery 1 in the solid state with a thin film includes a positive electrode 2 or cathode, a negative electrode 3 or anode, and an electrolyte 4 disposed therebetween.
In a preferred embodiment, the positive electrode 2, the electrolyte 4 and the negative electrode 3 are sequentially stacked to produce an electrochemical storage device. When the current collector (current collector) is connected to a prescribed load, the battery 1 discharges, causing lithium ions to be transferred from the anode (negative electrode) to the cathode (positive electrode) and electrons to be forced through the circuit.
According to the present invention, at least one of the positive electrode 2, the negative electrode 3, or the electrolyte 4 is defined by a thin film made of a ceramic material exhibiting ionic conductivity and electrical isolation.
Said film is preferably made of amorphous ceramic material, which is also an (independent) object of the present invention and better described below.
The thin film made of an inorganic amorphous material preferably contains an alkali metal, a metalloid, or a glass-forming nonmetal, and an anionic species.
The metalloid or metalloid is preferably an element from group 13, 14, 15 or 16 of the IUPAC periodic table.
The anionic species is preferably a chalcogen or from the nitrogen family.
The ionic species is preferably oxygen.
The alkali metal is preferably lithium or sodium.
In embodiments using lithium, an exemplary compound is LiBO2、LiPO3、Li6SiO7Li2GeO3、LiAlO2And Li2SO4. Polymorphs of the aforementioned compounds such as Li3BO3、Li4BO5、Li6B4O9、Li3B11O18、Li4P2O7、Li6Si2O7Is also an excellent example.
In embodiments where sodium is used, an exemplary compound is Na3BO3、Na3PO3、Na4SiO4、Li4GeO4、LiAlO2And Na2SO4. Polymorphs of the foregoing compounds are also excellentExamples are given. Doping the B site can improve performance. Examples include (1-x) LiBO2-xLi2SO4And (1-x) LiBO2-xLiPO3. Polymorphs of amorphous glass doped at the B-position can also be used.
Returning to the battery, in a preferred embodiment, the positive and negative electrodes 2, 3 and the electrolyte 4 are each defined by a thin film of ceramic material.
Alternatively, however, only the electrolyte 4 can be made of the thin ceramic membrane.
The thickness of the electrolyte 4 typically ranges from 100nm to 50 μm and is sufficiently continuous to prevent contact between the positive electrode 2 and the negative electrode 3.
The negative electrode 3 can be made of, for example, ceramics or organic/inorganic glasses with mixed ion/electron conducting properties, such as graphite, silicon alloys (Li)22Si4) Lithium titanium (Li)4Ti5O12) Lithium metal (Li) or indium (In).
However, in its preferred embodiment, the anode 3 is made of amorphous carbon (Li)xC6) And (4) preparing.
The positive electrode 2 can be made of, for example, an inorganic ceramic with mixed ionic/electronic conduction characteristics, preferably amorphous vanadium (V) oxide2O5) Lithium nickel manganese oxide (Li)2Mn3NiO8) Or alternatively lithium cobalt oxide (LiCoO)2) Or NCA (Li (NiCoAl) O2) And (4) preparing.
The electrolyte 4 can be made, for example, of an inorganic lithium ion conducting and electronically insulating ceramic.
The material used is preferably amorphous lithium metaborate (LiBo)2)。
Alternatively, however, it is also possible to use one of the following other compounds: amorphous lithium phosphate glass, amorphous lithium glass, lithium conductive garnet (such as LLZO, Li)7La3Zr2O12) Lithium phosphate (Li)3PO4) Or lithium sulfide (Li)2S)。
In other embodiments, the films listed above can be coated with other ceramic films,such as metal oxides for capacitors, such as RuO2And ZrSnTiO4Insulators such as ZrO2And Al2O3And so on.
The main aspect of the invention is that at least the electrolyte 4, but preferably also the positive electrode 2 and the negative electrode 4, has a carbon content ranging from 0.1 to 10%, more preferably ranging from 0.1 to 2%, in atomic percentage.
However, in the embodiments described herein, the carbon content is about 7% by atomic percentage.
In particular, unlike what can happen in known materials, the carbon particles 5 in the thin film according to the invention are uniformly distributed, with the possibility of still accidentally present carbon particles, so that the ceramic film is monolithic.
In other words, by inspecting the film by means of a suitable analytical technique, it is not possible to identify regions of distinctly different carbon concentration, except, of course, for small variations which are completely random.
The substrate (substrate) and the electrodes are prepared and then the electrolyte is deposited thereon in the form of a thin amorphous film, preferably by pyrolysis in flame spray (flame spray pyrolysis), due to which carbon particles 5 are seen uniformly distributed in the material.
Thus, a further electrode is deposited on top of the electrolyte 4 to form a current collector.
The invention achieves its intended objects and significant advantages are therefore obtained.
In fact, the production of solid-state batteries equipped with one or more superposed films prepared as described above is efficient (high performance) and at the same time economical.
In addition, the preparation of thin ceramic membranes composed of inorganic amorphous materials containing alkali metals, metalloids or glass-forming non-metals and anionic species makes the membranes extremely economical to produce.

Claims (17)

1. A solid-state battery comprising:
-a positive electrode (2);
-a negative electrode (3);
-an electrolyte (4) arranged between the positive electrode (2) and the negative electrode (3);
wherein said at least one of said positive electrode (2), said negative electrode (2) or said electrolyte (4) is defined by a thin film made of a ceramic material exhibiting ionic conductivity,
characterized in that said film is monolithic and has a carbon content ranging from 0.1% to 10% in atomic percentage.
2. The battery according to claim 1, wherein only the electrolyte (4) is defined by a thin monolithic film of ceramic material exhibiting high ionic conductivity and has a carbon content ranging from 0.1 to 10% in atomic percentage.
3. The battery according to claim 1, wherein the positive electrode (2) and the negative electrode (3) and the electrolyte (4) are each defined by a thin film of ceramic material.
4. A battery according to any preceding claim, wherein the thin film is made of an amorphous ceramic material exhibiting ionic conductivity.
5. A battery according to any one of the preceding claims, wherein the carbon content is defined by a plurality of carbon particles (5) uniformly distributed within the film.
6. A battery according to any preceding claim, wherein the negative electrode (3) is made of an organic or inorganic ceramic or glass material exhibiting mixed ionic/electronic conductivity.
7. A battery according to any one of the preceding claims, wherein the positive electrode (2) is made of an inorganic ceramic material exhibiting mixed ionic/electronic conductivity, preferably selected from the following:
lithium cobalt oxide (LiCoO)2)，
-NCA(Li(NiCoAl)O2)，
-LMNO(LiMn1.5Ni0.5O4)。
8. A battery according to any preceding claim, wherein the electrolyte (4) is made of an inorganic electronically insulating lithium ion conducting ceramic material.
9. A battery according to any one of the preceding claims, wherein the electrolyte (4) is made of amorphous lithium metaborate (LiBo 2).
10. A battery according to any preceding claim, wherein the film has a carbon content in atomic percent ranging from 0.1% to 2%.
11. The battery of any one of the preceding claims, wherein the film has at least 1x10-8Ionic conductivity of S/cm and less than 1x10-10Electron conductivity of S/cm.
12. A battery according to any preceding claim, wherein the film has a mass crystallinity of less than 10%.
13. A battery according to any preceding claim, wherein the film has a thickness of less than 10 microns.
14. A battery according to any preceding claim, wherein the thin film comprises an alkali metal, a metalloid, or a glass-forming non-metal and an anionic species.
15. The battery of claim 14, wherein the alkali metal is lithium or sodium.
16. The battery according to claim 14 or 15, wherein the metalloid or metalloid is classified as group 13, 14, 15 or 16 of the IUPAC periodic table.
17. The battery of any one of claims 14 to 16, wherein the anionic species is oxygen.
CN201980087550.2A 2018-11-07 2019-11-07 Solid-state battery Pending CN113853697A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT102018000010128A IT201800010128A1 (en) 2018-11-07 2018-11-07 SOLID STATE BATTERY
IT102018000010128 2018-11-07
PCT/IB2019/059564 WO2020095239A1 (en) 2018-11-07 2019-11-07 A solid-state battery

Publications (1)

Publication Number Publication Date
CN113853697A true CN113853697A (en) 2021-12-28

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EP (1) EP3878031A1 (en)
CN (1) CN113853697A (en)
IT (1) IT201800010128A1 (en)
WO (1) WO2020095239A1 (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4617105B2 (en) * 2003-07-23 2011-01-19 パナソニック株式会社 Coin-type all-solid-state battery
US9450239B1 (en) * 2012-03-15 2016-09-20 Erik K. Koep Methods for fabrication of intercalated lithium batteries
CN104659412B (en) * 2015-01-29 2017-05-10 中国科学院物理研究所 Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery
JP2016219130A (en) * 2015-05-15 2016-12-22 セイコーエプソン株式会社 Solid electrolyte battery, electrode assembly, composite solid electrolyte, and method for manufacturing solid electrolyte battery
JP7209169B2 (en) * 2017-04-27 2023-01-20 パナソニックＩｐマネジメント株式会社 solid electrolyte materials, electrode materials, positive electrodes, and batteries

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EP3878031A1 (en) 2021-09-15
WO2020095239A1 (en) 2020-05-14
IT201800010128A1 (en) 2020-05-07

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