CN113422103B - Interface layer for high-temperature solid lithium metal battery and preparation method - Google Patents

Interface layer for high-temperature solid lithium metal battery and preparation method Download PDF

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CN113422103B
CN113422103B CN202110685886.8A CN202110685886A CN113422103B CN 113422103 B CN113422103 B CN 113422103B CN 202110685886 A CN202110685886 A CN 202110685886A CN 113422103 B CN113422103 B CN 113422103B
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battery
molten salt
solid electrolyte
lithium metal
solid
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CN113422103A (en
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徐骏
宋虎成
叶义鹏
于智乾
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Nanjing University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • H01M2300/0048—Molten electrolytes used at high temperature
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

The invention discloses an interface layer for high-temperature solid lithium metal, which sequentially comprises a porous stainless steel current collector, a positive electrode, a solid electrolyte, a lithium metal negative electrode and a negative current collector from top to bottom; and when the battery is at high temperature, the molten salt is melted, and a three-phase interface layer is formed between the positive electrode and the solid electrolyte or a molten salt interface layer is formed between the negative electrode and the solid electrolyte.

Description

Interface layer for high-temperature solid lithium metal battery and preparation method
Technical Field
The invention relates to an interface modification technology for a high specific energy solid-state lithium metal battery, in particular to a design of a solid-state/all-solid-state lithium metal battery working at high temperature, belonging to the technical field of solar batteries.
Background
The existing lithium battery can only work at room temperature generally, however, at present, many devices need to work at low temperature or high temperature, such as a Mars detector and some special devices, and the batteries are not fully researched and applied. Compared with the traditional organic liquid battery, the solid-state lithium ion battery not only has great advantages in high energy density, safety and environmental friendliness, but also has good high-temperature operation performance. Various lithium ion batteries based on solid state electrolytes have been developed, such as those using perovskite, garnet, sulfide, etc., but still have certain problems at room temperature.
The poor interfacial charge transport capability of the electrolyte in solid-state batteries with low room temperature ionic conductivity makes it difficult to operate the batteries below room temperature. While the temperature plays a decisive role for the electrolyte and the ion transport at the interface. However, the solid-solid contact between the electrode and the solid electrolyte has poor ion transport ability, large interfacial contact resistance, and chemical side reactions of both at high temperature, resulting in a great decrease in battery capacity and life. Therefore, it is currently a great challenge to develop a lithium metal battery capable of operating in a high temperature environment.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problem and the defect that a solid lithium metal battery in the prior art is difficult to stably circulate at high temperature for a long time, the invention discloses a low-temperature ternary ultrathin molten salt interface layer to improve the interface stability of a solid electrolyte and metal lithium at high temperature, and simultaneously, a three-phase interface which is not limited by the dissolution of gas (oxygen, carbon dioxide and the like) is constructed at a positive electrode to obtain a high-specific-energy solid lithium-oxygen/carbon dioxide battery which can stably circulate at high temperature for a long time.
The technical scheme is as follows: an interfacial layer for a high temperature solid state lithium metal battery, characterized by: the lithium ion battery comprises a porous stainless steel current collector, a positive electrode, a solid electrolyte, a lithium metal negative electrode and a negative current collector from top to bottom in sequence;
and a molten salt layer is arranged between the positive electrode and the solid electrolyte and/or between the negative electrode and the solid electrolyte, the molten salt layer comprises a catalyst and molten salt arranged on the carbon cloth, and when the battery is at a high temperature, the molten salt is molten, and a three-phase interface layer is formed between the positive electrode and the solid electrolyte or a molten salt interface layer is formed between the negative electrode and the solid electrolyte under the action of the catalyst.
The invention further defines the technical scheme as follows: the molten salt comprises LiFSA-NaFSA, LiFSA-KFSA, LiFSA-RbFSA, LiFSA-CsFSA, NaFSA-KFSA, NaFSA-RbFSA, NaFSA-CsFSA, KFSA-RbFSA, KFSA-CsFSA, RbFSA-CsFSA low-temperature molten salt, ternary salt and inorganic alkali metal salt.
Further, the catalyst is a metal, metal oxide or N-doped carbon material nonmetal catalyst with a plasma effect.
Further, the anode is formed by compounding 5-90% by mass of lithium cobaltate, lithium manganate, lithium iron phosphate or ternary material, 3-80% by mass of lithium salt, 3-50% by mass of conductive agent and 3-15% by mass of binder;
or is compounded by 5 to 85 mass percent of sulfur active matter, 3 to 50 mass percent of conductive agent and 3 to 15 mass percent of binder;
or is compounded by 3 to 90 percent of electronic conductive agent, 3 to 90 percent of ion conductive electrolyte powder and 3 to 90 percent of catalyst by mass percentage.
Further, the solid electrolyte comprises perovskite/anti-perovskite ABO 3 Electrolyte, a ═ Ca, Sr, or La; b ═ Al or Ti, and an ionic conductivity of 10 -7 ～10 -3 Li of the NASICON type 1.5 Al 0.5 Ge 1.5 P 3 O 12 /Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 ，LAGP/LATP,10 -4 ～10 -3 S cm -1 Garnet type Li 7 La 3 Zr 2 O 12 ，LLZO,10 -4 ～10 - 3 S cm -1 Or sulfur-based electrolyte 10 -4 ～10 -2 S cm -1 。
Further, the negative electrode is at least one of an insertion type negative electrode, an alloy type negative electrode, and a conversion negative electrode.
Further, the negative current collector is a nano material compounded by carbon black, acetylene black, graphene, carbon nano tubes, ketjen black, carbon nano fiber carbon materials, metal materials of aluminum, ruthenium, gold, silver, copper, nickel and cobalt, corresponding metal oxides and one or more than two of semiconductor materials of silicon, germanium, tin and titanium dioxide.
The invention also discloses a preparation method of the interface layer for the high-temperature solid lithium metal battery, which is characterized by comprising the following steps of:
step one, according to the mass ratio of 2.4: 1: 6.2: 13.5 weighing Li 2 CO 3 、Al 2 O 3 、GeO 2 、NH 4 H 2 PO 4 The mixed powder of (1) was put in a ball mill at 400rmin -1 Ball milling for 6h, sintering at 900 deg.C for 6h, weighing 0.75g, pressing under 30MPa for 5min, and sintering at 900 deg.C for 6h to obtain the final productA solid lag ceramic electrolyte;
secondly, sputtering a layer of Ru metal serving as a catalyst on the carbon cloth through magnetron sputtering, wherein the sputtering power is 100W, the Ar rate is 40sccm, and the surface deposition thickness of the Ru metal is 10 nm;
thirdly, mixing the raw materials in a mass ratio of 1: 1.23: 1.83 LiNO was weighed 3 、KNO 2 、CsNO 3 Fully mixing, putting into a glove box, and fully melting and mixing the ternary salt at high temperature on a heating table;
and fourthly, coating molten salt on the solid electrolyte, and packaging the stainless steel current collector, the positive electrode, the solid electrolyte coated with the molten salt, the lithium metal negative electrode and the negative electrode current collector in sequence.
Has the advantages that: compared with the prior art, the interface layer design for the high-temperature solid lithium metal provided by the invention has the following advantages:
1) interface contact is improved through molten salt, interface resistance is reduced, and migration of Li & lt + & gt in an electrolyte and an interface is improved, so that the lithium ion battery can work at high temperature.
2) When the battery is at a high temperature, the molten salt melts to make the positive electrode and the LAGP fully contact, so that the interface impedance is reduced, and the lithium ion battery can be well circulated at the high temperature, as shown in figure 3.
3) The corresponding full charge/discharge capacity of the solid lithium-oxygen battery prepared on the basis of the interface layer reaches 1.58mAh cm at 150 DEG C -2 Corresponding to a coulombic efficiency close to 100%.
4) Having a thermochromic interface under light drive to absorb a wider spectrum of sunlight.
Drawings
FIG. 1 is a schematic diagram of a battery according to an embodiment of the present invention;
FIG. 2 is a schematic view of a Ru @ CC photo-thermal anode at room temperature in an embodiment of the invention.
FIG. 3 is a schematic graph of the cycling performance of a symmetrical cell at 150 ℃ in an example of the invention, where panel b is an enlarged view of Li/LAP/Li with molten salts in panel a.
Detailed Description
The invention is further elucidated with reference to the drawings and the embodiments.
As shown in fig. 1-2, the present embodiment provides an interfacial layer for high-temperature solid lithium metal, which comprises, in order from top to bottom, a porous stainless steel current collector, a positive electrode, a solid electrolyte, a lithium metal negative electrode, and a negative electrode current collector; and when the battery is at a high temperature, the molten salt melts, a three-phase interface layer is formed between the positive electrode and the solid electrolyte, and a molten salt interface layer is formed between the negative electrode and the solid electrolyte.
The embodiment also provides a preparation method of the interfacial layer for the high-temperature solid lithium metal, which specifically comprises the following steps:
step one, according to the mass ratio of 2.4: 1: 6.2: 13.5 weighing Li 2 CO 3 、Al 2 O 3 、GeO 2 、NH 4 H 2 PO 4 The mixed powder of (1) is put on a ball mill for 400r min -1 Ball milling for 6h, then sintering at 900 ℃ for 6h, then weighing 0.75g, pressing under 30MPa for 5min, and finally sintering at 900 ℃ for 6h again to form the solid LAGP ceramic electrolyte.
And secondly, sputtering a layer of Ru metal serving as a catalyst on the carbon cloth through magnetron sputtering, wherein the sputtering power is 100W, the Ar rate is 40sccm, and the surface deposition thickness of Ru is about 10 nm.
Thirdly, mixing the raw materials in a mass ratio of 1: 1.23: 1.83 LiNO was weighed 3 、KNO 2 、CsNO 3 And after fully mixing, putting the mixture into a glove box, and fully melting and mixing the ternary salt on a heating table at a high temperature.
And fourthly, coating molten salt on the solid electrolyte, and packaging the stainless steel current collector, the positive electrode, the molten salt coated solid electrolyte, the lithium metal negative electrode and the negative electrode current collector in sequence.
Preferably, the photothermal positive electrode in this embodiment may be made of lithium cobaltate, lithium manganate, lithium iron phosphate, ternary material such as LiNi for lithium ion battery 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.5 Co 0.2 Mn 0.3 O 2 ,LiNi 0.5 Co 0.2 Mn 0.2 O 2 ,LiNiCoMnO 2 ,LiNiCoAlO 2 5-90% of lithium salt such as LiBF4 and LiPF6, 5-95% of conductive agent such as one or a mixture of two or more of carbon black, acetylene black, SP, graphene, carbon nano-tubes, Ketjen black and carbon nano-fibers, 3-50% of conductive agent and 3-15% of binder such as PVDF and PVA.
Preferably, the positive electrode in this embodiment may be a positive electrode for a lithium-sulfur battery, which is formed by compounding 5% to 85% of a sulfur active material, 3% to 50% of one or a combination of two or more of a conductive agent such as carbon black, acetylene black, SP, graphene, a carbon nanotube, ketjen black, a carbon nanofiber, and the like, and 3% to 15% of a binder such as PVA or PVDF.
Preferably, the positive electrode in this embodiment may also be an ion-conductive electrolyte powder Li, which is a composite of one or two or more of an electron conductive agent such as carbon black, acetylene black, graphene, carbon nanotubes, ketjen black, carbon nanofibers, etc., in a proportion of 3% to 95%, for a lithium-gas battery such as a lithium-air, lithium-oxygen, lithium-carbon dioxide, lithium-nitrogen battery, and the like 1.5 Al 0.5 Ge 1.5 P 3 O 12 /Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 、Li 7 La 3 Zr 2 O 12 、Perovskite/Antiperovskite ABO 3 A ═ Ca, Sr, La; al and Ti in 3-95 wt% and catalyst such as Ru and RuO 2 ,Au,Fe、Ni、Co、RuO 2 NiO transition metal compound, non-noble metal catalyst, N-doped carbon material and other non-metal catalyst in 3-100 wt%.
Preferably, the lithium battery in the embodiment of the present invention includes conventional lithium-gas batteries, solid lithium metal batteries, solid lithium-sulfur batteries, solid lithium-air batteries, solid lithium-oxygen batteries, solid lithium-carbon dioxide batteries, solid lithium-nitrogen batteries, and related batteries including molten salt batteries, lithium-gas batteries, and the like, and hybrid batteries thereof.
Preferably, the preparation method of the positive electrode and the current collector in this embodiment may be physical vapor deposition, chemical vapor deposition, hydrothermal synthesis, or other chemical synthesis methods.
Preferably, the electrolyte sheet material may be one or a composite of two or more of powder, nanoparticles, nanowires, and nanosheets.
Preferably, the negative electrode in this embodiment may be an intercalation type carbon, graphene, TiO 2 、LiTiO 2 Alloys of Si, Ge, Sn, Al, transition type Fe 2 O 3 、CuO、CoO 2 And the like, or a combination of two or more thereof.
Preferably, the negative electrode current collector in this embodiment includes a nanomaterial in which one or more of carbon black, acetylene black, Graphene (Graphene), Carbon Nanotubes (CNT), ketjen black, carbon nanofiber carbon material, metal materials such as aluminum, ruthenium, gold, silver, copper, nickel, and cobalt, and corresponding metal oxides, and semiconductor materials such as silicon, germanium, tin, and titanium dioxide are combined.
The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the protection scope of the invention.

Claims (5)

1. An interfacial layer for a high temperature solid state lithium metal battery, characterized by: the battery sequentially comprises a porous stainless steel current collector, a positive electrode, a solid electrolyte, a lithium metal negative electrode and a negative current collector from top to bottom;
a molten salt layer is arranged between the positive electrode and the solid electrolyte and between the negative electrode and the solid electrolyte, the molten salt layer between the positive electrode and the solid electrolyte comprises a catalyst and molten salt arranged on carbon cloth, when the battery is at high temperature, the molten salt is molten, and a three-phase interface layer is formed between the positive electrode and the solid electrolyte under the action of the catalyst;
the catalyst is a metal, metal oxide or N-doped carbon material nonmetal catalyst with a plasma effect; the lithium metal battery is a lithium-gas battery.
2. The interfacial layer for a high temperature solid state lithium metal battery of claim 1, wherein: the solid electrolyte comprises perovskite/anti-perovskite ABO 3 Electrolyte, a = Ca, Sr, or La; b = Al or Ti.
3. The interfacial layer for a high temperature solid state lithium metal battery of claim 1, wherein: the molten salt comprises LiFSA-NaFSA, LiFSA-KFSA, LiFSA-RbFSA, LiFSA-CsFSA, NaFSA-KFSA, NaFSA-RbFSA, NaFSA-CsFSA, KFSA-RbFSA, KFSA-CsFSA, RbFSA-CsFSA low-temperature molten salt, ternary salt and inorganic alkali metal salt.
4. The interfacial layer for a high temperature solid state lithium metal battery of claim 1, wherein: the negative current collector is a nano material compounded by one or more than two of silicon, germanium, tin and titanium dioxide semiconductor materials.
5. A preparation method of an interface layer for a high-temperature solid-state lithium-oxygen battery is characterized by comprising the following steps:
step one, according to the mass ratio of 2.4: 1: 6.2: 13.5 weighing Li 2 CO 3 、Al 2 O 3 、GeO 2 、NH 4 H 2 PO 4 The mixed powder of (1) was put in a ball mill at 400rmin -1 Ball-milling for 6h, then sintering for 6h at 900 ℃, then weighing 0.75g, pressing for 5min under the pressure of 30MPa, and finally sintering for 6h at 900 ℃ again to form the solid LAGP ceramic electrolyte;
secondly, sputtering a layer of Ru metal serving as a catalyst on the carbon cloth through magnetron sputtering, wherein the sputtering power is 100W, the Ar rate is 40sccm, and the surface deposition thickness of the Ru metal is 10 nm;
thirdly, mixing the raw materials in a mass ratio of 1: 1.23: 1.83 LiNO was weighed 3 、KNO 2 、CsNO 3 Fully mixing, putting into a glove box, and fully melting and mixing the ternary salt at high temperature on a heating table;
and fourthly, coating molten salt on the solid electrolyte, and packaging the stainless steel current collector, the positive electrode, the solid electrolyte coated with the molten salt, the lithium metal negative electrode and the negative electrode current collector in sequence.
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Citations (5)

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JP2009029846A (en) * 2007-07-24 2009-02-12 Nissan Motor Co Ltd Electrolyte, electrode catalyst layer, fuel cell and method for producing them
US8795868B1 (en) * 2013-03-13 2014-08-05 Melvin H. Miles Rechargeable lithium-air and other lithium-based batteries using molten nitrates
CN108155412A (en) * 2017-12-26 2018-06-12 暨南大学 A kind of inorganic-inorganic hybrid solid-state electrolyte ceramic membrane and preparation method thereof
CN109713402A (en) * 2018-12-28 2019-05-03 南京大学 It can be in the solar energy optical-thermal lithium battery and preparation method thereof that temperature range limit works
CN111799513A (en) * 2020-07-11 2020-10-20 浙江锋锂新能源科技有限公司 Diaphragm-free quasi-solid battery and preparation method of composite pole piece thereof

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US9431672B2 (en) * 2012-05-16 2016-08-30 Worcester Polytechnic Institute Molten-salt electrolyte unitized regenerative hydrogen-halogen fuel cell with anion transfer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009029846A (en) * 2007-07-24 2009-02-12 Nissan Motor Co Ltd Electrolyte, electrode catalyst layer, fuel cell and method for producing them
US8795868B1 (en) * 2013-03-13 2014-08-05 Melvin H. Miles Rechargeable lithium-air and other lithium-based batteries using molten nitrates
CN108155412A (en) * 2017-12-26 2018-06-12 暨南大学 A kind of inorganic-inorganic hybrid solid-state electrolyte ceramic membrane and preparation method thereof
CN109713402A (en) * 2018-12-28 2019-05-03 南京大学 It can be in the solar energy optical-thermal lithium battery and preparation method thereof that temperature range limit works
CN111799513A (en) * 2020-07-11 2020-10-20 浙江锋锂新能源科技有限公司 Diaphragm-free quasi-solid battery and preparation method of composite pole piece thereof

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