CN110767894A - Solid electrolyte-lithium complex, method for preparing same, and all-solid lithium secondary battery comprising same - Google Patents
Solid electrolyte-lithium complex, method for preparing same, and all-solid lithium secondary battery comprising same Download PDFInfo
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Abstract
The invention discloses a solid electrolyte-lithium complex, a preparation method thereof and an all-solid-state lithium secondary battery comprising the same. The solid electrolyte-lithium composite body of the present invention includes a solid electrolyte and a lithium-containing layer compounded on a first main surface of the solid electrolyte, the lithium-containing layer being formed by applying a lithium-containing substrate in a molten state onto the first main surface or vapor-depositing the lithium-containing substrate onto the first main surface, the lithium-containing substrate including metallic lithium or a lithium alloy. The invention can accurately control the thickness of the lithium-containing layer (as a lithium cathode), and can solve the problem of contact between the lithium metal cathode and the solid electrolyte, improve the interface resistance, contribute to the capacity exertion of the battery and improve the cycle performance of the battery.
Description
Technical Field
The invention belongs to the field of energy batteries, and particularly relates to a part for a lithium battery, in particular to an all-solid-state lithium secondary battery and a preparation method thereof.
Background
Lithium ion batteries have high energy density and good cycling stability, and have been widely used in portable electronic devices, electric vehicles and power grid energy storage. The conventional lithium ion battery generally takes graphite as a negative electrode material, and the working principle of the lithium ion battery is that lithium ions are separated/embedded between positive and negative electrode layered active substance layers, but the specific capacity limit of the graphite type negative electrode material is about 372mAh/g, so that the energy density of the lithium ion battery is difficult to further improve based on the negative electrode material, and the lithium ion battery is difficult to adapt to the requirement of the market on the lithium ion battery with higher energy density.
For this reason, development of an anode material having a higher specific capacity is required. Lithium metal has the lowest potential (-3.04V vs. hydrogen target), extremely high energy density (3860mAh/g), and the lightest density (0.534 g/cm)3) And is an ideal anode material selection. The lithium metal is used as the cathode to form a battery with the anode of the conventional lithium ion battery, so that the quality of the cathode is reduced, the irreversible consumption of lithium ions in the first charging process can be made up, the output voltage of the battery is improved, and the energy density (500wh/kg) of the battery is greatly improved; in addition, the lithium metal itself is used as a lithium source in the battery, and the battery can be formed by combining with certain high-specific-capacity and low-cost cathode materials, so that the battery has higher energy density, for example, a lithium-sulfur battery (2600wh/kg) and a lithium-air battery (5210 wh/kg).
Although lithium metal represents a great advantage, it has not been commercialized, mainly because: (1) the preparation method of the metal lithium cathode with the precisely controllable thickness is lacked, so that the waste of the metal lithium is avoided, and the utilization rate of the cathode is improved; (2) in the process of metal lithium circulation, an electrolyte/metal lithium interface continuously evolves, so that the internal resistance of the battery is increased, and the circulation performance is poor; (3) although the solid electrolyte can effectively solve the problem of interface sustained reaction, the interface contact is a serious challenge for the solid battery, and at present, the lithium metal cathode is usually bonded to the solid electrolyte by a hot pressing method, so that holes still appear at the interface, the interface resistance is large, and the battery capacity is difficult to exert.
In view of the above problems, how to develop a lithium metal negative electrode with precisely controlled thickness and high interface stability is an important challenge for application of lithium metal as a negative electrode of a lithium battery.
Disclosure of Invention
The present invention has an object to provide a lithium-containing material having a precisely controlled thickness and a stable interface, which can be directly used as a negative electrode of an all solid-state lithium secondary battery, and a method for preparing the same.
One aspect of the present invention provides a solid electrolyte-lithium composite body, the solid electrolyte including a first major surface on which a lithium-containing layer is composited and a second major surface opposite thereto, the lithium-containing layer being formed by applying a lithium-containing substrate in a molten state on the first major surface or vapor-depositing the lithium-containing substrate on the first major surface, the lithium-containing substrate including metallic lithium or a lithium alloy.
The first major surface and the second major surface of the solid electrolyte are opposed, the surface compounded with the lithium-containing layer is referred to as a first major surface which is opposed to the cathode when the battery is assembled, and the surface opposite to the first major surface is referred to as a second major surface which is opposed to the anode when the battery is assembled.
In certain embodiments, the lithium-containing layer has a thickness of 0.001 to 100 μm, preferably 0.1 to 100 μm, more preferably 1 to 100 μm, and most preferably 5 to 25 μm; the width is 0.1 to 3000mm, preferably 1 to 3000mm, more preferably 10 to 3000mm, most preferably 50 to 600 mm.
In certain embodiments, the lithium alloy comprises, in addition to the element Li, at least one alloying component of Ag, Al, Au, Ba, Fe, Na, K, Mg, Si, Sn, Sr, Ti, Zn and Zr, wherein the mass percent of lithium is between 10% and 99.99%.
In certain embodiments, the solid-state electrolyte comprises a polymeric solid-state electrolyte and/or an inorganic solid-state electrolyte, optionally with the addition of one or more lithium salts of: lithium perchlorate, lithium nitrate, lithium bistrifluoromethylsulfonimide and lithium bistrifluorosulfonimide. Preferably, the solid electrolyte includes a polymer solid electrolyte to which a lithium salt is added, or an inorganic solid electrolyte.
In certain embodiments, the polymer solid electrolyte comprises one or more of the following: polyethylene oxide, polyvinylidene fluoride, polyacrylate, polyvinyl carbonate, polymethacrylic acid and polyacrylonitrile; the inorganic solid electrolyte includes one or more of the following: a garnet-structured lithium lanthanum zirconium oxide, an oxide-structured lithium phosphorus oxynitride, a sulfide-structured lithium sulfur phosphorus compound, or a (trans) perovskite type.
Another aspect of the present invention provides an all-solid-state lithium secondary battery comprising the above-described solid electrolyte
In certain embodiments, a metal foil is attached as a negative current collector or tab on the side of the lithium-containing layer opposite the solid electrolyte; preferably, the metal foil comprises a copper foil, a nickel foil or a molybdenum foil.
In certain embodiments, the positive electrode material of the all-solid-state lithium secondary battery includes at least one material selected from the group consisting of: lithium iron phosphate (LiFePO)4) Lithium oleate (LiMn)2O4) Lithium cobaltate (LiCoO)2) Lithium nickel cobalt manganese oxide (LiNiCoMnO)2) Lithium nickel cobalt aluminate (LiNi)xCoyAlzO2) (0 < x, y, z < 1, x + y + z ═ 1), sulfur carbon, air, vanadium pentoxide.
In certain embodiments, sulfur carbon comprises a mixture of elemental sulfur and carbon materials including carbon nanotubes, graphene, activated carbon, ketjen black, and the like.
In certain embodiments, the battery shape is selected from one of the following: button cell, cylindrical, steel-shelled square, aluminium-shelled square, laminate polymer battery, linear battery, flexible battery of can buckling.
Still another aspect of the present invention provides a method for preparing the above solid electrolyte-lithium composite body, the method comprising:
heating the lithium substrate to 1500 ℃ at 250 ℃ and preferably 700 ℃ in an environment filled with a gas (including an inert gas such as argon) that is not reactive with lithium, and then coating the molten lithium substrate on the first major surface of the solid electrolyte surface, preferably by a casting method, at a coating speed of 0.1 to 10 m/min; or
At a vacuum degree of 10-1～10-5Pa, preferably 10-2～10-3The lithium substrate is vaporized and deposited on the first major surface of the solid electrolyte surface in a vacuum chamber of Pa at a temperature of 500-1200 deg.C, preferably 600-800 deg.C, preferably by roll-to-roll deposition at a rate of 0.01-20m/min, preferably 1-15 m/min.
Compared with the prior art, the solid electrolyte-lithium complex and the preparation method thereof provided by the invention can effectively solve the problems of processing and forming of ultrathin metal lithium and matching with the current battery process, and simplify the battery assembly process. In the all-solid-state battery with higher energy density and better safety, the method can effectively improve the interface resistance of the battery, reduce the polarization of the battery and improve the energy density of the battery.
Drawings
Fig. 1 is an SEM image of a cross section of example 1 in which metallic lithium in a molten state was coated on the surface of a solid electrolyte.
Fig. 2 is a charge/discharge curve of a lithium-sulfur battery assembled using a solid electrolyte-lithium composite formed by applying metallic lithium in a molten state on the surface of a solid electrolyte in example 1.
Fig. 3 is an SEM image of lithium metal deposited on the surface of the solid electrolyte by means of vacuum physical deposition in example 2.
FIG. 4 is the charge and discharge curve of the button cell assembled by the way of vacuum physical deposition of metallic lithium on the metallic lithium negative electrode prepared by solid-state electrolysis in example 2.
Fig. 5 is a charge and discharge curve (curve 1) of an all solid-state lithium battery assembled by depositing a lithium magnesium alloy on a solid electrolyte by vacuum physical deposition in example 3 and a charge and discharge curve of an all solid-state lithium battery using a metal lithium foil as a negative electrode in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Further, the following examples are exemplary in terms of various product structure parameters, various reaction participants and process conditions, but through a lot of experiments, the inventors of the present invention have verified that other different structure parameters, other types of reaction participants and other process conditions listed above are applicable and can achieve the claimed technical effects.
Example 1
Mixing lithium lanthanum zirconium oxide powder (Shenzhenjnace Jingzhida science and technology Co., Ltd.), polyvinylidene fluoride (Azadine reagent Co., Ltd.) and polyacrylonitrile (Azadine reagent Co., Ltd.) in ethanol solution, coating on a stainless steel substrate, and drying to obtain the solid electrolyte. Then, in an argon glove box, molten metallic lithium was coated on the surface of the solid electrolyte. Fig. 1 is an SEM image of a cross section of the solid electrolyte surface obtained in this example. As can be seen from the figure, the thickness of the lithium metal layer was about 3 μm, the contact between the solid electrolyte and the lithium metal was good, and no voids were present.
Mixing elemental sulfur (Aladdin reagent Co., Ltd.) and multi-walled carbon nanotubes (Shandong Dazhang nanometer Co., Ltd.) in a mass ratio of 3: 1, then placing the mixture in a vacuum oven, heating to 160 ℃, wherein the vacuum degree of the oven is-0.1 MPa, and heating for 6 hours to obtain a mixture, wherein the mixture is mixed with acetylene black (national group chemical reagent, Inc.), polyvinylidene fluoride (Aladdin reagent, Inc.) and lithium bistrifluoromethylsulfonate imide (Aladdin reagent, Inc.) according to the mass ratio of 7: 1: 1: 1 in methyl pyrrolidone, 12h, coating the slurry on an aluminum foil with a thickness of 200 microns, and then drying in a vacuum oven at 80 ℃.
The solid electrolyte-lithium metal complex in example 1 was combined with the positive electrode prepared as above to constitute a button cell. Fig. 2 is a charge-discharge curve of the Li-S battery, from which it is seen that the battery exhibits a charge-discharge plateau of the Li-S battery, with a normal voltage plateau.
Example 2
Polyethylene oxide (molecular weight 60 ten thousand, avastin reagent limited), and lithium bistrifluoromethylenesulfonamide (avastin reagent limited) were mixed in a molar ratio of 8: stirring in acetonitrile solution, coating on a stainless steel substrate, and drying to obtain the solid electrolyte. Then put into a thermal evaporation chamber (Shenyang scientific instruments, Inc. of Chinese academy of sciences) where the arc current for evaporating lithium is 80A, the temperature is 750 deg.C, and the vacuum pressure is 10-3Pa, the evaporation time is 100min, and a lithium layer with the thickness of 3 mu m is formed on the surface of the solid electrolyte. Fig. 3 is an SEM image of a lithium negative electrode fabricated by vacuum physical deposition in this example, and from the figure, it can be seen that the metallic lithium is uniformly deposited on the surface of the solid electrolyte. Is the lithium metal-solid electrolyte bulk prepared in example 2 and a lithium iron phosphate positive plate (Suzhoucha New energy science and technology Co., Ltd., areal density of 10 mg/cm)2) And forming the button cell. The battery charging curve is shown in fig. 4, and the voltage plateau is normal.
Example 3
Mixing lithium sulfur phosphorus powder (Shenzhenjinejinzhida science and technology Co., Ltd.) and polymethyl methacrylate (Aladdin reagent Co., Ltd.) in a dimethylformamide solution, coating on a stainless steel substrate, and drying to obtain the solid electrolyte. Then the alloy is put into a thermal evaporation chamber (Shenyang scientific instruments, Inc. of Chinese academy of sciences), the arc current for evaporating lithium-magnesium alloy (the mass fraction of lithium is 95%, the magnesium is 5%) is 120A, the temperature is 850 ℃, and the vacuum pressure is 10-3Pa, vapor deposition time of 120min, in solid stateA lithium layer with a thickness of 10 μm was formed on the electrolyte surface. And a lithium nickel cobalt manganese oxide positive plate (Suzhou Na New energy science and technology Co., Ltd., areal density of 14 mg/cm)2) And assembling the whole solid soft package battery.
Comparative example 1
An all-solid-state pouch cell was assembled using the same solid electrolyte and positive electrode as in example 3, and 50 μm lithium metal foil as the negative electrode.
As apparent from fig. 5 in which the open curve is the charge and discharge curve of the all-solid battery in example 3 and the solid curve is the charge and discharge curve of the all-solid battery in comparative example 1, the voltage polarization of the all-solid battery in example 3 is significantly lower than that of the all-solid battery in comparative example 1, and thus the all-solid battery in example 3 can exert a higher capacity. In view of this, the deposition of metallic lithium on the surface of the solid electrolyte allows to significantly improve the contact, reduce the interfacial resistance and avoid the loss of capacity of the battery due to polarization.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A solid electrolyte-lithium composite body, characterized in that the solid electrolyte comprises a first main surface on which a lithium-containing layer is composited and a second main surface opposite thereto, the lithium-containing layer being formed by applying a lithium-containing substrate in a molten state on the first main surface or vapor-depositing a lithium-containing substrate on the first main surface, the lithium-containing substrate comprising metallic lithium or a lithium alloy.
2. The solid electrolyte-lithium composite according to claim 1, wherein the lithium-containing layer has a thickness of 0.001 to 100 μm, preferably 0.1 to 100 μm, more preferably 1 to 100 μm; the width is 0.1 to 3000mm, preferably 1 to 3000mm, more preferably 10 to 3000 mm.
3. The solid electrolyte-lithium composite body according to claim 1, wherein the lithium alloy contains, in addition to the element Li, at least one alloy component of Ag, Al, Au, Ba, Fe, Na, K, Mg, Si, Sn, Sr, Ti, Zn, and Zr, wherein the mass percentage of lithium is 10% to 99.99%.
4. The solid electrolyte-lithium composite of claim 1, wherein the solid electrolyte comprises a polymer solid electrolyte and/or an inorganic solid electrolyte, optionally with the addition of one or more lithium salts of: lithium perchlorate, lithium nitrate, lithium bistrifluoromethylsulfonimide and lithium bistrifluorosulfonimide.
5. The solid electrolyte-lithium composite of claim 4, wherein the polymer solid electrolyte comprises one or more of: polyethylene oxide, polyvinylidene fluoride, polyacrylate, polyvinyl carbonate, polymethacrylic acid and polyacrylonitrile; the inorganic solid state electrolyte includes one or more of: a garnet-structured lithium lanthanum zirconium oxide, an oxide-structured lithium phosphorus oxynitride, a sulfide-structured lithium sulfur phosphorus compound, or a (trans) perovskite type.
6. An all-solid-state lithium secondary battery characterized by comprising the solid electrolyte-lithium composite according to any one of claims 1 to 5 as a solid electrolyte and a negative electrode.
7. The all solid-state lithium secondary battery according to claim 6, wherein a metal foil is attached as a negative electrode current collector or a tab on a side of the lithium-containing layer opposite to the solid electrolyte; preferably, the metal foil comprises a copper foil, a nickel foil or a molybdenum foil.
8. The all-solid lithium secondary battery according to claim 6, wherein the positive electrode material comprises at least one material selected from the group consisting of: lithium iron phosphate (LiFePO)4) Lithium oleate (LiMn)2O4) Lithium cobaltate (LiCoO)2) Lithium nickel cobalt manganese oxide (LiNiCoMnO)2) Lithium nickel cobalt aluminate (LiNi)xCoyAlzO2) (0 < x, y, z < 1, x + y + z ═ 1), sulfur carbon, air, vanadium pentoxide.
9. The all-solid lithium secondary battery according to claim 6, wherein a battery shape is selected from one of the following: button cell, cylindrical, steel-shelled square, aluminium-shelled square, laminate polymer battery, linear battery, flexible battery of can buckling.
10. A method of preparing the solid electrolyte-lithium composite body of claim 1, comprising:
heating the lithium substrate to 1500 ℃ in an environment filled with a gas which is not reactive with lithium, and then coating the molten lithium substrate on the first main surface of the solid electrolyte, preferably by a tape casting method at a coating speed of 0.1-10 m/min; or
At a vacuum degree of 10-1～10-5In a vacuum chamber of Pa, the lithium substrate is vaporized and deposited on the first main surface of the solid electrolyte surface at a temperature of 500-1200 deg.C, preferably, roll-to-roll deposition is carried out at a rate of 0.01-20 m/min.
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| CN201810824824.9A CN110767894A (en) | 2018-07-25 | 2018-07-25 | Solid electrolyte-lithium complex, method for preparing same, and all-solid lithium secondary battery comprising same |
| PCT/CN2018/101931 WO2020019392A1 (en) | 2018-07-25 | 2018-08-23 | Solid electrolyte-lithium composite, preparation method therefor, and all-solid-state lithium secondary battery comprising same |
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| CN108134049B (en) * | 2017-12-19 | 2023-06-30 | 成都大超科技有限公司 | Negative electrode layer, preparation method thereof, lithium battery cell and lithium battery |
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| CN108110217A (en) * | 2017-12-19 | 2018-06-01 | 成都亦道科技合伙企业（有限合伙） | A kind of solid state lithium battery composite negative pole and preparation method thereof |
| CN108321355A (en) * | 2018-03-28 | 2018-07-24 | 中能中科（天津）新能源科技有限公司 | Lithium an- ode prefabricated component and preparation method thereof, lithium an- ode and lithium metal secondary cell |
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