CN114883641A - LATP-based solid electrolyte interface layer and preparation method of LATP-based solid lithium battery - Google Patents

LATP-based solid electrolyte interface layer and preparation method of LATP-based solid lithium battery Download PDF

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Publication number
CN114883641A
CN114883641A CN202210500083.5A CN202210500083A CN114883641A CN 114883641 A CN114883641 A CN 114883641A CN 202210500083 A CN202210500083 A CN 202210500083A CN 114883641 A CN114883641 A CN 114883641A
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latp
lithium
interface layer
solid electrolyte
boron nitride
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朱蕾
胡文斌
汤卫平
陈玉华
吴勇民
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Shanghai Institute of Space Power Sources
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Shanghai Institute of Space Power Sources
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M10/052—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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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 invention discloses a preparation method of a LATP-based solid electrolyte interface layer and a LATP-based solid lithium battery, which comprises the following steps: drying commercial boron nitride release agent slurry into powder, placing the powder around the LATP cold pressing sheet, and sintering at high temperature to enable the powder to cover the surface of the LATP cold pressing sheet to form the interface layer. The solid lithium battery solves the problem that in the LATP-based solid lithium battery, Ti4+ in the LATP solid electrolyte is easy to be reduced by metal lithium, so that the interface problem is caused, the battery is invalid, and the LATP solid electrolyte cannot be widely applied.

Description

LATP-based solid electrolyte interface layer and preparation method of LATP-based solid lithium battery
Technical Field
The invention relates to the field of solid-state batteries, in particular to a LATP-based solid electrolyte interface layer and a preparation method of a solid-state battery.
Background
In recent 30 years, the rapid development of lithium ion batteries has led to its dominance in the field of energy storage, and has gradually extended its range of use from portable devices to electronic vehicles, energy storage power stations, military equipment, and the like. However, the market presents more challenges and requirements for high energy density and safe reliability. Lithium metal is considered to be an ideal material for replacing commercial graphite for high energy density batteries due to its extremely high theoretical capacity and low oxidation-reduction potential. However, unstable solid electrolyte interfaces in liquid organic electrolytes and the growth of lithium dendrites present low coulombic efficiency and safety problems. Especially recently, the safety problem frequently occurring in lithium ion batteries has attracted more and more attention. Solid-state batteries, which are generally considered as the final solution, use a solid-state electrolyte instead of a flammable small molecule liquid electrolyte, which can prevent lithium dendrite penetration due to high young's modulus and excellent mechanical properties. However, as research progresses, more and more research reports that side reactions at the interface between solid-state battery components, particularly electrolytes in contact with lithium metal, may pose safety issues, even thermal runaway.
The NASICON structure solid electrolyte is considered to be a promising structure. They have superior air stability compared to polymers, sulfides and other oxides, and are easy and low cost to prepare. Specifically, in the NASICON structure solid electrolyte, LATP has 10 because of its -4 ～10 -3 S cm -1 Are of particular interest because of their high ionic conductivity. Despite many benefits, LATP still faces a deadly short plate, Ti 4+ Will be reduced to Ti by lithium in LATP 3+ . Instability to lithium limits the electrochemical stability window, increases grain boundary resistance, forms cracks between adjacent ion channels, and ultimately leads to battery failure. To realize the practical application of LATP, researchers have generally improved lithium stability from three aspects: (1) and (4) doping elements. Ge (germanium) oxide 4+ Is commonly used forBy partial or complete substitution of Ti 4+ And has higher ion conductivity and excellent mechanical strength to prevent penetration of lithium dendrites. However, due to Ge 4+ The same reduction reaction occurs with Li, and the high cost of germanium metal and germanium compounds, which is not an ideal strategy; (2) and (3) modifying the surface of the inorganic substance. Covering LATP with Al 2 O 3 Inorganic layers such as ZnO and BN to avoid direct contact with lithium. (LIU Yulong, SUN Qian, ZHAO Yang, et al.Stabilizing the interface of the NASICON solid electrolyte membrane Li metal with atomic layer deposition [ J].ACS Applied Materials&Interfaces, 2018, 10 (37): 31240-. In addition, rigid coatings can also introduce more serious interfacial problems; (3) and (3) modifying the surface of the polymer. This approach not only separates LATP from Li, but also mitigates interface contact resistance, thanks to the electronic insulation and flexibility of the polymer. However, the weight and thickness of the polymer layer will have an impact on the cell energy density. (YU Shiching, SCHMOHL, LIU Zigen, et al, instruments in a layered hybrid electrolyte and its application in a long life span all-solid-state lithium batteries [ J]Journal of Materials Chemistry a, 2019, 7 (8): 3882-3894.) therefore, there is a need to find a simple, low-cost LATP modification method while balancing effective protection with low interfacial resistance.
Disclosure of Invention
The invention aims to solve the problem that in a LATP-based solid-state lithium battery, Ti4+ in a LATP solid-state electrolyte is easy to be reduced by metal lithium, so that the interface problem is caused, the battery is invalid, and the LATP solid-state electrolyte cannot be widely applied.
In order to achieve the above object, the present invention provides a method for producing an LATP-based solid electrolyte interface layer, comprising: drying commercial boron nitride release agent slurry into powder, placing the powder around the LATP cold pressing sheet, and sintering at high temperature to enable the powder to cover the surface of the LATP cold pressing sheet to form the interface layer.
Optionally, the commercial boron nitride release agent includes at least boron nitride dispersed in an acetone solvent, a binder, and an emulsifier.
Optionally, the boron nitride is a sheet structure and the binder is a tubular structure.
Optionally, the interfacial layer is formed in-situ on the LATP cold pressed sheet surface during high temperature sintering.
Optionally, the interfacial layer is a dense three-dimensional multilayer structure.
Optionally, the interface layer has a thickness of 2 μm to 4 μm.
The invention also provides a preparation method of the LATP-based solid-state lithium battery, which comprises the following steps: on the LATP solid electrolyte, an interface layer is processed by the preparation method, and after a metallic lithium negative electrode is processed on one side of the solid electrolyte containing the interface layer, the metallic lithium negative electrode and a positive electrode are assembled into a solid lithium battery.
Optionally, the method of processing lithium metal comprises: and (5) evaporation.
Optionally, in the process of evaporating the metal lithium, the metal lithium reacts with the boron nitride to generate lithium nitride. .
Optionally, the lithium metal negative electrode has a thickness of 2 μm to 5 μm.
The invention has the beneficial effects that:
(1) the commercialized boron nitride release agent containing inorganic boron nitride, organic binder and emulsifier is applied to the interface layer of the solid-state battery, and the organic-inorganic composite interface layer is formed on the surface of the solid-state electrolyte sheet in one step, so that the soft substance is used for reducing the interface impedance of the solid-state battery, and the inorganic rigid filler is used for improving the mechanical strength of the interface layer. The raw materials are easy to obtain, the cost is low, and the method is simple to operate.
(2) The compact interface layer with a three-dimensional multilayer structure is formed, so that the solid electrolyte LATP and the metal lithium cathode can be isolated, the reduction reaction is avoided, the local current density and the interface resistance are effectively reduced in the subsequent working process of the battery, the uniform Li + deposition/stripping is brought, and the problem of lithium dendrite is effectively avoided.
(3) The lithium metal cathode in the solid lithium battery provided by the invention is formed by adopting a lithium evaporation mode, lithium steam reacts with boron nitride in an interface layer in the lithium evaporation process, and lithium nitride with high ionic conductivity and strong lithium compatibility is generated at the interface, so that the solid lithium battery with excellent capacity exertion, cycle performance and rate performance is obtained.
(4) The good thermal conductivity of boron nitride in the interface layer can enable heat to be diffused quickly, the safety problem of LATP-based solid metal lithium is solved, and thermal runaway is avoided.
Drawings
FIG. 1 is an electron micrograph of an interfacial layer prepared in example 1 of the present invention.
Fig. 2 is an optical photograph of a solid electrolyte containing an interface layer and a solid electrolyte not containing an interface layer prepared in example 1 of the present invention after evaporation of a lithium negative electrode.
Fig. 3 is a graph showing XPS test results of the interface layer prepared in example 2 of the present invention.
Fig. 4 is a graph showing the cycle performance of the solid lithium battery prepared in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides an internal structure of a solid-state lithium battery.
The anode is at least one of lithium cobaltate, lithium manganate, lithium iron phosphate, a nickel-cobalt-manganese ternary material, a nickel-cobalt-aluminum ternary material and a lithium-rich manganese-based material. The solid electrolyte is a LATP-based oxide ceramic wafer with the chemical formula of Li 1+x Al x Ti 2-x (PO 4 ) 3 (x＝0～0.4)。
The interfacial layer was formed by spraying a commercial boron nitride release agent onto the solid electrolyte surface. The commercial boron nitride release agent is mainly formed by dispersing boron nitride, a binder and an emulsifier in an acetone solvent. Optionally, the binder comprises any one or a combination of two of sodium carboxymethyl cellulose and styrene butadiene rubber; the emulsifier is one or more of alkyl benzene sulfonate (sodium dodecyl benzene sulfonate), quaternary ammonium salt and alkyl sulfate (sodium dodecyl sulfate). The interfacial layer helps to improve lithium stability and in-situ formation of Li3N at the interface provides high ionic conductivity and low resistance for LATP lithium batteries.
The commercial boron nitride release agent used in the invention is purchased from Dongguan Jiadan chemical Co., Ltd, model JD-3028, named as Jiadan boron nitride release spray, batch 2021/09/26.
The preparation method of the invention comprises the following steps:
(1) LATP-BASED SOLID ELECTROLYTE INTERFACE LAYER
Step 1: preparing a LATP cold pressing tablet;
step 2: drying commercial boron nitride release agent slurry into powder, placing the powder around the LATP cold pressing sheet, and sintering at high temperature to enable the powder to cover the surface of the LATP cold pressing sheet to form the interface layer.
Because the LATP cold pressing sheet has pores, and the pores disappear during high-temperature sheet burning, the wafer can be reduced and deformed, so that the defects are supplemented by a powder burying step before high-temperature sintering in the process of solid electrolyte ceramic sheet burning. The prior art generally adopts solid electrolyte powder as powder when the powder is buried. The invention adopts commercial boron nitride release agent which is dried into powder as powder for embedding powder. The commercial boron nitride release agent at least comprises boron nitride with a sheet structure dispersed in an acetone solvent, a binder with a tubular structure and an emulsifier. The binder in the release agent can resist the high temperature of 1200 ℃, can not volatilize in the sintering process, can ensure that the release agent is coated more firmly, and forms an interface layer with a compact three-dimensional multilayer structure on the surface of the LATP cold pressing sheet in situ, thereby having better coating effect. The interface layer is directly formed on the LATP cold-pressed sheet during sintering, so that the interface layer can be well contacted with the LATP and completely attached without gaps. The interface layer is formed by stacking two-dimensional flaky boron nitride and is firmly coated by matching with a binder. Preferably, the thickness of the interfacial layer is 2 μm to 4 μm.
The interface layer with a compact three-dimensional multilayer structure is a lithium-philic structure, and lithium can penetrate into the interface layer containing boron nitride to generate lithium nitride, so that the lithium nitride in the solid lithium battery is only on the surface of the interface layer, and lithium can still be conducted even if the interface layer has a certain thickness.
(2) Solid-state battery
Step 1: preparing a positive pole piece;
step 2: obtaining a metallic lithium negative electrode on one side of the LATP solid electrolyte containing the interface layer by adopting a lithium evaporation mode;
and step 3: and assembling the positive electrode and the solid electrolyte/interface layer/negative electrode into a solid lithium battery.
Preferably, the thickness of the lithium metal anode is 2 μm to 5 μm.
Example 1
(1) LATP-BASED SOLID ELECTROLYTE INTERFACE LAYER
Step 1: putting solid electrolyte powder into an agate mortar, manually grinding for half an hour, adding a proper amount of 3% PVB ethanol solution, grinding again until the solvent is completely volatilized, weighing about 0.8g of powder, putting the powder into a mold, keeping the powder for 20min under the pressure of 10MPa, and pressing the powder into a solid wafer with the diameter of 10mm to obtain a LATP cold pressing sheet.
Step 2: flatly placing the LATP cold-pressed sheet into a crucible, spreading a commercial boron nitride release agent dried into powder around the LATP cold-pressed sheet, placing the LATP cold-pressed sheet into a tube furnace, heating to 960 ℃ at the speed of 5 ℃/min, preserving heat for 12h, and forming an interface layer on the LATP-based solid electrolyte.
(2) Solid-state battery
Step 1: 77 wt.% of nickel cobalt lithium manganate positive electrode material, 10 wt.% of carbon black, 10 wt.% of polyvinylidene fluoride (PVDF) and 3 wt.% of LiClO 4 Dispersing in N-methyl-2-pyrrolidone (NMP), mixing, coating the slurry on aluminum foil, drying in a forced air oven at 80 deg.C for 6 hr, and transferringTransferring the positive plate to a vacuum oven at 110 ℃ for drying for 24 hours to obtain a positive plate;
step 2: obtaining a metallic lithium negative electrode by adopting a lithium evaporation mode on one side of the LATP solid electrolyte containing the interface layer, wherein the thickness of the metallic lithium negative electrode layer is 2 mu m;
and step 3: and (3) filling the positive electrode, the solid electrolyte/interface layer/the lithium layer into a button cell stainless steel shell in a stacking mode, assembling the button cell in a glove box, and testing, wherein in order to eliminate the contact impedance between the positive electrode and the solid electrolyte, a trace amount of liquid electrolyte is dropwise added at the interface between the positive electrode and the solid electrolyte.
The scanning electron micrograph of the interface layer prepared in example 1 is shown in fig. 1, and it is seen that the thickness of the interface layer is less than 3 μm, which is much smaller than the thickness of a general polymer coating, and does not greatly affect the energy density of the battery. The interface layer is a compact three-dimensional multilayer structure, can cover all surfaces of the LATP sheet to completely separate LATP and Li, and can effectively reduce local current density and interface resistance by the three-dimensional structure.
An optical photograph of the solid electrolyte/lithium prepared by this example 1 is shown in fig. 2, and in order to verify the performance of the interface layer, the LATP ceramic sheet was experimentally divided into two parts, one part being the exposed LATP and the other part being the LATP containing the interface layer. After deposition of lithium by evaporation, a portion of the unprotected LATP turned completely black, indicating that a reduction reaction occurred, while the other half of the protected LATP was covered with bright Li metal, again demonstrating the protective effect of the interface layer on the LATP.
Example 2
(1) LATP-based solid electrolyte interfacial layer
Step 1: putting solid electrolyte powder into an agate mortar, manually grinding for half an hour, adding a proper amount of 3% PVB ethanol solution, grinding again until the solvent is completely volatilized, weighing about 0.8g of powder, putting the powder into a mold, keeping the powder for 20min under the pressure of 10MPa, and pressing the powder into a solid wafer with the diameter of 10mm to obtain a LATP cold pressing sheet.
And 2, step: flatly placing the LATP cold-pressed sheet into a crucible, spreading a commercial boron nitride release agent dried into powder around the LATP cold-pressed sheet, placing the LATP cold-pressed sheet into a tube furnace, heating to 960 ℃ at the speed of 5 ℃/min, preserving heat for 12h, and forming an interface layer on the LATP-based solid electrolyte.
(2) Preparation of solid-state lithium battery
Step 1: 77 wt.% of lithium iron phosphate cathode material, 10 wt.% of carbon black, 10 wt.% of polyvinylidene fluoride (PVDF) and 3 wt.% of LiClO 4 Dispersing in N-methyl-2-pyrrolidone (NMP), uniformly mixing, coating the slurry on an aluminum foil, drying in a blast oven at 80 ℃ for 6 hours, and then transferring to a vacuum oven at 110 ℃ for drying for 24 hours to obtain a positive pole piece;
step 2: obtaining a metallic lithium negative electrode on one side of the solid electrolyte sheet containing the interface layer LATP by adopting a lithium evaporation mode, wherein the thickness of a metallic lithium negative electrode layer is 5 mu m;
and step 3: and (3) filling the positive electrode, the solid electrolyte/interface layer/the lithium layer into a button cell stainless steel shell in a stacking mode, assembling the button cell in a glove box, and testing, wherein in order to eliminate the contact impedance between the positive electrode and the solid electrolyte, a trace amount of liquid electrolyte is dropwise added at the interface between the positive electrode and the solid electrolyte.
The result of XPS test of the interface layer prepared in example 2 is shown in FIG. 3, in which BN and Li were simultaneously observed at the interface after evaporation of lithium 3 N, demonstrating the formation of lithium nitride.
The cycle curve of the solid-state lithium battery prepared in the embodiment 2 is shown in fig. 4, the battery is subjected to charge and discharge cycles at a current density of 15mA/g and a voltage range of 2.5-4.2V at room temperature, the first discharge specific capacity is 152.3mAh/g, the capacity is kept unchanged after 50 cycles, the capacity exertion and the cycle stability are excellent, and the solid-state lithium battery is expected to be applied to the fields of energy storage power supplies, power batteries and the like.
In summary, in the invention, a commercialized boron nitride release agent is introduced to the interface between the LATP solid electrolyte and the lithium metal, and the main components contained in the release agent are utilized to form an organic-inorganic composite three-dimensional compact interface protection layer, so that the interface resistance is reduced, the generation of lithium dendrites is avoided, and the lithium battery can be used for a long timeFormation of Li with high ionic conductivity at the interface 3 N, multiple purposes, so that the LATP-based solid-state lithium battery shows excellent performance.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.

Claims (10)

1. A method for preparing an LATP-based solid electrolyte interfacial layer, comprising: drying commercial boron nitride release agent slurry into powder, placing the powder around the LATP cold pressing sheet, and sintering at high temperature to enable the powder to cover the surface of the LATP cold pressing sheet to form the interface layer.
2. The production method according to claim 1, wherein the commercial boron nitride release agent comprises at least boron nitride dispersed in an acetone solvent, a binder, and an emulsifier.
3. The method of claim 2, wherein the boron nitride has a sheet structure and the binder has a tubular structure.
4. The method of claim 1 wherein said interfacial layer is formed in situ on the surface of said LATP cold pressed sheet during high temperature sintering.
5. The method of claim 1, wherein the interfacial layer is a dense three-dimensional multilayer structure.
6. The method according to claim 1, wherein the interface layer has a thickness of 2 μm to 4 μm.
7. A method for manufacturing a LATP-based solid-state lithium battery, comprising: on a LATP solid electrolyte, an interface layer is processed by the production method according to any one of claims 1 to 6, and after the metallic lithium negative electrode is processed on the side of the solid electrolyte containing the interface layer, a solid lithium battery is assembled with the positive electrode.
8. The method of claim 7, wherein the processing lithium metal comprises: and (5) evaporation.
9. The method according to claim 8, wherein the lithium metal reacts with the boron nitride to form lithium nitride during evaporation of the lithium metal.
10. The method of claim 7, wherein the lithium metal negative electrode has a thickness of 2 μm to 5 μm.
CN202210500083.5A 2022-04-22 2022-04-22 LATP-based solid electrolyte interface layer and preparation method of LATP-based solid lithium battery Pending CN114883641A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115224368A (en) * 2022-08-16 2022-10-21 西安交通大学 Solid electrolyte and lithium cathode integrated battery assembly, lithium solid battery and preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115224368A (en) * 2022-08-16 2022-10-21 西安交通大学 Solid electrolyte and lithium cathode integrated battery assembly, lithium solid battery and preparation method
CN115224368B (en) * 2022-08-16 2023-12-19 西安交通大学 Solid electrolyte and lithium cathode integrated battery assembly, lithium solid battery and preparation method

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