CN108232108B - Lithium battery positive electrode structure, preparation method thereof and lithium battery structure - Google Patents
Lithium battery positive electrode structure, preparation method thereof and lithium battery structure Download PDFInfo
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- 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
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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
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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
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Abstract
The invention relates to the technical field of lithium batteries, in particular to a lithium battery positive electrode structure, a preparation method thereof and a lithium battery structure. The lithium battery positive electrode structure comprises a positive electrode current collector and a positive electrode film layer formed on the positive electrode current collector, wherein the positive electrode film layer comprises a positive electrode material, and a transition layer and a modification layer are sequentially formed on one side, far away from the positive electrode current collector, of the positive electrode film layer. The transition layer is arranged on the positive electrode film layer, so that the interface impedance between the positive electrode film and the modification layer can be effectively reduced, the modification layer on the transition layer can effectively prevent the electrolyte from directly contacting with the positive electrode film layer, the irreversible reaction between trace HF in the electrolyte and a positive electrode battery structure containing the modification layer is avoided, meanwhile, the collapse of the positive electrode structure layer under high-voltage charging is inhibited, and the reversible capacity and the circularity of a battery manufactured by using the positive electrode structure layer are improved.
Description
[ field of technology ]
The invention relates to the technical field of lithium batteries, in particular to a lithium battery positive electrode structure, a preparation method thereof and a lithium battery structure.
[ background Art ]
The lithium battery has the advantages of high energy density and output working voltage, and is widely used in the aspects of digital electronic products, electric automobiles, large-scale energy storage and the like. The positive electrode material is an important component of the lithium battery, and directly influences the parameters of the lithium battery such as capacity, cycle performance and the like. Common positive electrode materials include lithium iron phosphate, lithium cobaltate, lithium manganate, ternary materials and the like. But at high voltages, the positive electrode material structure can irreversibly collapse, resulting in rapid capacity decay. In addition, in the process of charging and discharging a lithium battery, a layer of solid electrolyte interface film (SEI film) is generated on the surface of the electrode, the main component of the SEI film is a lithium compound, and the stable SEI film can effectively prevent organic macromolecules from entering the electrode material structure to enhance the stability of the electrode, so that the cycle performance of the battery is effectively improved, but a part of lithium loss is caused at the same time, so that how to generate the stable SEI film is to solve LiCoO 2 High performance key problems such as high capacity, high voltage, high energy and the like of the battery.
[ invention ]
In order to solve the problems that the current lithium ion positive electrode structure is easy to collapse irreversibly, so that the electric energy capacity of the ion battery structure is low and the charge-discharge cycle effect is poor, the invention provides the lithium battery positive electrode structure with stable structure, high specific energy and good charge-discharge cycle effect and a preparation method thereof.
In order to solve the technical problems, the invention provides a technical scheme that:
the lithium battery anode structure comprises an anode current collector and an anode film layer formed on the anode current collector, wherein the anode film layer comprises an anode material, and a transition layer and a modification layer are sequentially formed on one side, far away from the anode current collector, of the anode film layer; the transition layer is sputtered together by a lithium cobalt oxide target and a fast ion conductor target so as to be formed on the positive electrode film layer; the modification layer is formed on the transition layer by performing annealing treatment after being sputtered by a fast ion conductor target material singly;
the fast ion conductor is Li 1+y A y Ti 2-x-y M x (PO 4 ) 3 、La 2/3-x Li 3x TiO 3 Any one of them; wherein in Li 1+ y A y Ti 2-x-y M x (PO 4 ) 3 In (a): x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, x+y is more than or equal to 0 and less than or equal to 2, A is any one of Al, ga, in, sc, Y, and M is any one of Ge, zr and Hf; in La 2/3-x Li 3x TiO 3 In (a): x is more than 0.05 and less than 0.167.
Preferably, the thickness of the transition layer is 50-100nm, and the thickness of the modification layer is 10-60nm.
In order to solve the technical problems, the invention provides a further technical scheme:
a method for preparing the positive electrode structure of the lithium battery comprises the following steps:
forming a positive electrode film layer on the positive electrode current collector by using a magnetron sputtering method;
sequentially forming a transition layer and a modification layer on one side, far away from the positive current collector, of the positive film layer by utilizing a magnetron sputtering method, wherein the transition layer comprises a positive electrode material and a fast ion conductor which are contained in the positive film layer, and the modification layer comprises a fast ion conductor;
the transition layer is sputtered together by a lithium cobalt oxide target and a fast ion conductor target so as to be formed on the positive electrode film layer; the modification layer is formed on the transition layer by performing annealing treatment after being sputtered by a fast ion conductor target material singly;
the fast ion conductor is Li 1+y A y Ti 2-x-y M x (PO 4 ) 3 、La 2/3-x Li 3x TiO 3 Any one of them; wherein in Li 1+ y A y Ti 2-x-y M x (PO 4 ) 3 In (a): x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, x+y is more than or equal to 0 and less than or equal to 2, and A is any one of Al, ga, in, sc, Y; m is one of Ge, zr and Hf; in La 2/3-x Li 3x TiO 3 In (a): x is more than 0.05 and less than 0.167.
Further, the step of forming the positive electrode thin film layer on the positive electrode current collector by using the magnetron sputtering method specifically comprises the following steps:
providing a positive electrode current collector as a substrate;
installing an anode film layer target material;
vacuum was applied to 5 x 10 -4 Pa or less;
heating the substrate holder to a temperature of 100-400 ℃;
and (3) regulating the air pressure to be 0.5-1.5Pa, the ratio of argon to oxygen to be 7:3-9:1, and the sputtering power to be 80-120W, and sputtering for 2 hours to obtain the positive electrode film layer formed on the positive electrode current collector.
Preferably, the gas pressure is 1.0Pa, the ratio of argon to oxygen: 9:1, sputtering power is: 120W.
And sequentially forming a transition layer and a modification layer on one side, far away from the positive current collector, of the positive film layer by utilizing a magnetron sputtering method, wherein the transition layer comprises a positive electrode material and a fast ion conductor which are included in the positive film layer, and the modification layer comprises a fast ion conductor and comprises the following specific steps:
mounting lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 A target material;
mounting a positive electrode thin film layer formed on a positive electrode current collector on a substrate holder;
vacuum was applied to 5 x 10 -4 Pa or less;
heating the substrate holder to a temperature of 100-400 ℃;
the sputtering is carried out by adjusting the air pressure to be 0.5 Pa to 1.0Pa, the ratio of argon to oxygen to be 7:3 to 9:1 and the sputtering power to be 80W to 120W;
lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 Sputtering the target materials together for 30min to obtain a transition layer formed on the positive electrode film layer;
fast ion conductor Li 0.33 La 0.56 TiO 3 Sputtering the target material for 30min independently;
and annealing at 400 ℃ for 3 hours to obtain the modification layer formed on the transition layer.
Preferably, lithium cobaltate (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 Lithium cobalt oxide (LiCoO) during co-sputtering of targets 2 ) Sputtering power of the target material is 120W, and the fast ion conductor Li 0.33 La 0.56 TiO 3 The sputtering power of the target is as follows: 100W; fast ion conductor Li 0.33 La 0.56 TiO 3 The sputtering power of the target material for sputtering alone for 30min is 100W.
Preferably, lithium cobaltate (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 The ratio of argon to oxygen in the process of target co-sputtering is changed according to the following gradient, and the ratio is as follows: under argon: oxygen=9:1, 8:2, and 7:3 for 10 minutes each.
Preferably, it is a third object of the present invention to provide a lithium battery structure comprising the positive electrode structure of a lithium battery as described above, a negative electrode structure disposed opposite to the positive electrode structure, and an electrolyte layer between the positive electrode structure and the negative electrode structure.
Compared with the prior art, the transition layer is arranged on the positive electrode film layer, so that the interface impedance between the positive electrode film layer and the modification layer can be effectively reduced, the modification layer on the transition layer can effectively prevent the electrolyte from directly contacting with the positive electrode film layer, the irreversible reaction between trace HF in the electrolyte and the positive electrode structure containing the positive electrode film layer is avoided, and meanwhile, the collapse of the positive electrode structure under high-voltage charging is restrained, so that the reversible capacity and the circularity of a battery manufactured by utilizing the positive electrode structure are improved.
The transition layer comprises a positive electrode material contained in the positive electrode film layer, and meanwhile, the transition layer contains a fast ion conductor contained in the modification layer, so that a good transition effect is achieved between the positive electrode film layer and the modification layer, the lattice matching property between the positive electrode film layer and the modification layer can be well enhanced, the interface impedance between the positive electrode film layer and the modification layer is reduced, the conduction performance of conductive ions between the modification layer and the positive electrode film layer is enhanced, and the conductivity of an electrode structure containing the transition layer is further improved.
The thickness of the transition layer is 50-100nm, so that the interface effect between the modification layer and the positive electrode film layer can be well reduced, and the interface impedance is reduced.
The thickness of the modification layer is 10-60nm. The thickness of the surface modification layer is within the range of 10-60nm, so that the electrolyte and the transition layer can be separated, and meanwhile, the conductivity of the conductive ions in the electrolyte and the positive electrode film layer can be ensured.
And forming the transition layer and the modification layer on the positive electrode film layer by utilizing a magnetron sputtering method, wherein the transition layer comprises lithium cobaltate and a fast ion conductor, and the modification layer comprises the fast ion conductor, so that a denser surface modification layer can be obtained.
Lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 Lithium cobalt oxide (LiCoO) during co-sputtering of targets 2 ) Sputtering power of the target material is 120W, and the fast ion conductor Li 0.33 La 0.56 TiO 3 The sputtering power of the target is as follows: 100W. Lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 The ratio of argon to oxygen in the process of target co-sputtering is changed according to the following gradient, and the ratio is as follows: under argon: oxygen=9:1, 8:2, and 7:3 for 10 minutes each. The transition layer structure formed by sputtering is compact.
It is a third object of the present invention to provide a lithium battery structure comprising the above-described positive electrode structure of a lithium battery and an electrolyte layer. The lithium battery has high structural stability and good charge-discharge cycle effect.
[ description of the drawings ]
FIG. 1 is a schematic diagram of the overall structure of a positive electrode structure of a lithium battery in the invention;
FIG. 2 is a flow chart of the present invention for forming a positive electrode thin film layer over the positive electrode current collector;
FIG. 3 is a flow chart of the present invention for sputtering a transition layer and a finishing layer onto a positive film layer;
fig. 4 is a schematic view of the overall structure of the lithium battery of the present invention.
[ detailed description ] of the invention
For the purpose of making the technical solution and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1, a positive electrode structure 30 of a lithium battery, the positive electrode structure 30 of the lithium battery includes a positive electrode current collector 1001 and a positive electrode thin film layer 1002 formed on the positive electrode current collector 1001, the positive electrode thin film layer 1002 includes a positive electrode material, and a transition layer 1003 and a modification layer 1004 are sequentially formed on a side of the positive electrode thin film layer 1002 away from the positive electrode current collector 1001.
The current collector refers to a structure or a part for collecting current, and mainly refers to metal foils such as copper foil and aluminum foil on the ion battery, and the general meaning of the current collector can comprise a tab. The main function is to collect the current generated by the active material of the battery so as to form a larger current output to the outside, so that the current collector should be in sufficient contact with the active material and the internal resistance should be as small as possible. The current collector is generally divided into a positive current collector and a negative current collector, wherein an aluminum foil is generally adopted as the positive current collector and a copper foil is adopted as the negative current collector in the lithium battery material. Specifically, aluminum is easily oxidized, a compact oxide film is easily formed on the surface of the aluminum to protect the aluminum from oxidation, the stable potential is high, lithium ions are easily intercalated into a low-potential negative electrode, and the aluminum is not suitable for being used as a negative electrode current collector. Copper oxidizes at high potential and is not suitable for use as a positive current collector. In the present invention, the positive electrode current collector 1001 used is aluminum foil.
The positive electrode thin film layer 1002 formed on the positive electrode current collector 1001 includes a positive electrode material selected from layered LiCoO 2 (lithium cobalt oxide), liNi x Co y M 1-x-y O 2 (0<x ≤1, 0 ≤y<1. And 0 (0)<x+y.ltoreq.1, m=al, mn, etc.).
Preferably, the positive electrode material of the positive electrode thin film layer 1002 is mainly lithium cobalt oxide (LiCoO) 2 ). Lithium cobalt oxide (LiCoO) 2 ) The product has good cycle stability, good reversibility, high specific capacity and convenient preparation, and is widely used in various fields. Meanwhile, the electrochemical performance of lithium cobaltate is superior, the battery polarization can be well inhibited, the thermal effect is less, the rate performance is improved, and the positive current collector 1001 can be well protected from being corroded by electrolyte.
In the first charge and discharge process of the liquid lithium battery, the electrode material (comprising the positive electrode structure layer and the negative electrode material layer) reacts with the electrolyte on the solid-liquid phase interface to form a passivation layer covering the surface of the electrode material. The passivation layer is an interfacial layer, has the characteristics of a solid electrolyte, is an electronic insulator, but is Li + Excellent conductor of Li + Can be freely inserted and removed through the passivation layer, and thus the passivation film is called a "solid electrolyte interface film" (solid electrolyte interface) SEI film for short. The SEI film can effectively prevent macromolecular solvent from entering through the positive electrode film layer 1002 and entering the positive electrode current collector 1001, protect an electrode structure and enhance the circularity, but the process can cause lithium loss. In addition, the conventional electrolyte contains a trace amount of hydrofluoric acid (HF), which is mainly due to the presence of trace amount of moisture in the electrolyte, and the hydrofluoric acid (HF) reacts with the electrode structure and the SEI film, so that the SEI film is unstable; while easily causing the electrode structure to be corroded, causing it to collapse. Therefore, a transition layer 1003 and a finishing layer 1004 are formed on the positive electrode thin film layer 1002 as an artificial SEI film.
The transition layer 1003 includes the same positive electrode material as the positive electrode thin film layer 1002 includes, and the transition layer 1003 further includes a fast ion conductor. That is, when the positive electrode thin film layer 1002 contains lithium cobalt oxide (LiCoO) 2 ) As a positive electrode material, lithium cobalt oxide (LiCoO) is correspondingly contained in the transition layer 1003 2 ）。
The modification layer 1004 includes the same fast ion conductor as in the transition layer 1003, and the fast ion conductors included in the transition layer 1003 and the modification layer 1004 are Li 1+y A y Ti 2-x-y M x (PO 4 ) 3 (0.ltoreq.x.ltoreq.2, 0.ltoreq.y.ltoreq.2 and 0.ltoreq.x+y.ltoreq.2, A= Al, ga, in, sc, Y, M=Ge, zr, hf, etc.), la 2/3-x Li 3x TiO 3 (0.05 < x < 0.167).
Fast ion conductor: also known as super ionic conductors, sometimes referred to as solid electrolytes, the most essential feature of which is that they differ from the usual ionic conductors in that they have an ionic conductivity (1 x 10) in a certain temperature range comparable to that of liquid electrolytes -3 S/cm) and low ion conductivity activation energy (. Ltoreq.0.40 eV).
Preferably, in the present invention, the transition layer 1003 includes a fast ion conductor, specifically Li 0.33 La 0.56 TiO 3 。Li 0.33 La 0.56 TiO 3 The solid electrolyte has the highest ionic conductivity (1 mS/cm) in the solid electrolyte, can effectively improve the conduction rate of lithium ions and improves the conductivity of the positive electrode structural layer.
In the present invention, the fast ion conductor included in the modification layer 1004 is the same as the fast ion conductor included in the transition layer 1003, and is Li 0.33 La 0.56 TiO 3 。
In the present invention, the transition layer 1003 includes the positive electrode material included in the positive electrode film 1002, and includes the fast ion conductor included in the modification layer 1004, which plays a good role in transition between the positive electrode film 1002 and the modification layer 1004, and can well enhance the lattice matching between the positive electrode film 1002 and the modification layer 1004, reduce the interface impedance between the positive electrode film 1002 and the modification layer 1004, enhance the conductivity of conductive ions between the modification layer 1004 and the positive electrode film 1002, and further enhance the conductivity of the electrode structure including the transition layer 1003.
The modification layer 1004 is used as an artificial SEI film, so that direct contact between electrolyte and the positive electrode film 1002 is well avoided, loss of lithium ions in a charging cycle process can be well reduced, coulomb effect of first charge and discharge is improved, energy density is improved, adverse side reactions between the positive electrode film 1002 and an electrolyte contact interface are inhibited, and stability of a positive electrode structure is effectively improved. Meanwhile, collapse of the positive electrode structure caused by lithium ion release in the high-voltage charging process can be restrained, stability of the positive electrode structure is enhanced, and cycle performance of the battery is improved. In the present invention, the off voltage of the positive electrode structure layer after the formation of the transition layer 1003 and the modification layer 1004 can be 4.5V.
The second purpose of the invention is to provide a preparation method of the positive electrode structure of the lithium battery.
The preparation method of the positive electrode structure of the lithium battery comprises the following steps:
v1: forming a positive electrode film layer on the positive electrode current collector by using a magnetron sputtering method;
v2: and sequentially forming a transition layer and a modification layer on one side, far away from the positive current collector, of the positive film layer by utilizing a magnetron sputtering method, wherein the transition layer comprises a positive electrode material and a fast ion conductor which are included in the positive film layer, and the modification layer comprises a fast ion conductor.
Referring to fig. 2, in the above step, in the step V1, a cathode thin film layer 1002 is formed on a cathode current collector 1001 by using a magnetron sputtering method, and lithium cobalt oxide (LiCoO) is selected in the present embodiment 2 ) The method is described as a specific positive electrode material, and specifically comprises the following steps:
v11: providing a positive electrode current collector as a substrate;
v12: installing an anode film layer target material;
v13: vacuum was applied to 5 x 10 -4 Pa or less;
v14: heating the substrate holder to a temperature of 100-400 ℃;
v15: and (3) regulating the air pressure to be 0.5-1.5Pa, the ratio of argon to oxygen to be 7:3-9:1, and the sputtering power to be 80-120W, and sputtering for 2 hours to obtain the positive electrode thin film layer 1002 formed on the positive electrode current collector 1001.
In the above step V11, the positive electrode current collector 1001 is fixed on the substrate holder of the magnetron sputtering chamber;
in the above V13, the target material of the positive electrode thin film layer is lithium cobalt oxide (LiCoO) 2 ）。
In the above step V15, sputtering is performed at a gas pressure of preferably 1.0Pa, a ratio of argon to oxygen of preferably 9:1, and a sputtering power of preferably 120W, and the thickness of the resulting positive electrode thin film layer 1002 is 200 to 400nm.
Referring to fig. 3, in the step V2, the transition layer 1003 and the modification layer 1004 are sequentially formed on the positive electrode thin film 1002 at a side far from the positive electrode current collector 1001 by using a magnetron sputtering method, and in this embodiment, a positive electrode material lithium cobalt oxide (LiCoO) is specifically selected 2 ) And a fast ion conductor Li 0.33 La 0.56 TiO 3 The specific steps are as follows:
v21: mounting lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 A target material;
v22: mounting a positive electrode thin film layer formed on a positive electrode current collector on a substrate holder;
v23: vacuum was applied to 5 x 10 -4 Pa or less;
v24: heating the substrate holder to a temperature of 100-400 ℃;
v25: the sputtering is carried out by adjusting the air pressure to be 0.5 Pa to 1.0Pa, the ratio of argon to oxygen to be 7:3 to 9:1 and the sputtering power to be 80W to 120W;
v26: lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 Sputtering the targets together for 30min to obtain a transition layer 1003 formed on the positive electrode film layer 1002;
v27: fast ion conductor Li 0.33 La 0.56 TiO 3 Sputtering the target material for 30min independently;
v28: annealing was performed at 400 c for 3 hours to obtain a modified layer 1004 formed over the transition layer 1003.
Preferably, in step V26, lithium cobaltate (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 Lithium cobalt oxide (LiCoO) during co-sputtering of targets 2 ) The sputtering power of the target material is preferably 120W, and the fast ion conductor Li 0.33 La 0.56 TiO 3 The sputtering power of the target is preferably: 100W.
Preferably, in step V26, lithium cobaltate (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 The ratio of argon to oxygen in the process of target co-sputtering is changed according to the following gradient, and the ratio is as follows: under argon: oxygen=9:1, 8:2, and 7:3 for 10 minutes each.
Preferably, in step V27: fast ion conductor Li 0.33 La 0.56 TiO 3 The sputtering power of the target material for sputtering alone for 30min is preferably 100W.
The thickness of the transition layer 1003 obtained in the step V26 is 50-100nm, and the thickness of the modification layer 1004 obtained in the step 28 is 10-60nm.
Referring to fig. 4, a third objective of the present invention is to provide a lithium battery structure 10, wherein the lithium battery structure 10 includes the above-mentioned positive electrode structure 30, a negative electrode structure layer 400 and an electrolyte layer 300 disposed between the negative electrode structure layer 400 and the positive electrode structure 30. The electrolyte layer 300 employed in the present invention includes lithium salt LiPF 6 、LiBF 4 Any one of them. Wherein the negative electrode structure layer 400 includes a negative electrode current collector layer 4002 and a negative electrode thin film layer 4001 formed on the negative electrode current collector layer 4002, a copper foil used in the present invention is used as the negative electrode current collector layer 4002, and the positive electrode thin film layer 1002 and the negative electrode thin film layer 4001 are disposed in opposition.
Compared with the prior art, the transition layer is arranged on the positive electrode film layer, so that the interface impedance between the positive electrode film layer and the modification layer can be effectively reduced, the modification layer on the transition layer can effectively prevent the electrolyte from directly contacting with the positive electrode film layer, the irreversible reaction between trace HF in the electrolyte and the positive electrode structure containing the positive electrode film layer is avoided, and meanwhile, the collapse of the positive electrode structure under high-voltage charging is restrained, so that the reversible capacity and the circularity of a battery manufactured by utilizing the positive electrode structure are improved.
The transition layer comprises a positive electrode material contained in the positive electrode film layer, and meanwhile, the transition layer contains a fast ion conductor contained in the modification layer, so that a good transition effect is achieved between the positive electrode film layer and the modification layer, the lattice matching property between the positive electrode film layer and the modification layer can be well enhanced, the interface impedance between the positive electrode film layer and the modification layer is reduced, the conduction performance of conductive ions between the modification layer and the positive electrode film layer is enhanced, and the conductivity of an electrode structure containing the transition layer is further improved.
The thickness of the transition layer is 50-100nm, so that the interface effect between the modification layer and the positive electrode film layer can be well reduced, and the interface impedance is reduced.
The thickness of the modification layer is 10-60nm. The thickness of the surface modification layer is within the range of 10-60nm, so that the electrolyte and the transition layer can be separated, and meanwhile, the conductivity of the conductive ions in the electrolyte and the positive electrode film layer can be ensured.
And forming the transition layer and the modification layer on the positive electrode film layer by utilizing a magnetron sputtering method, wherein the transition layer comprises lithium cobaltate and a fast ion conductor, and the modification layer comprises the fast ion conductor, so that a denser surface modification layer can be obtained.
Lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 Lithium cobalt oxide (LiCoO) during co-sputtering of targets 2 ) The sputtering power of the target material is preferably 120W, and the fast ion conductor Li 0.33 La 0.56 TiO 3 The sputtering power of the target is preferably: 100W. Lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 The ratio of argon to oxygen in the process of target co-sputtering is changed according to the following gradient, and the ratio is as follows: under argon: oxygen=9:1, 8:2, and 7:3 for 10 minutes each. The transition layer structure formed by sputtering is compact.
It is a third object of the present invention to provide a lithium battery structure comprising the above-described positive electrode structure of a lithium battery and an electrolyte layer. The lithium battery has high structural stability and good charge-discharge cycle effect.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements, etc. within the principles of the present invention should be included in the scope of the present invention.
Claims (9)
1. A lithium battery positive electrode structure is characterized in that: the lithium battery anode structure comprises an anode current collector and an anode film layer formed on the anode current collector, wherein the anode film layer comprises an anode material, a transition layer and a modification layer are sequentially formed on one side, far away from the anode current collector, of the anode film layer, and the transition layer is sputtered together by a lithium cobalt oxide target and a fast ion conductor target so as to be formed on the anode film layer; the modification layer is formed on the transition layer by performing annealing treatment after being sputtered by a fast ion conductor target material singly;
the fast ion conductor is Li 1+y A y Ti 2-x-y M x (PO 4 ) 3 、La 2/3-x Li 3x TiO 3 Any one of them; wherein in Li 1+ y A y Ti 2-x-y M x (PO 4 ) 3 In (a): x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, x+y is more than or equal to 0 and less than or equal to 2, and A is any one of Al, ga, in, sc, Y; m is one of Ge, zr and Hf; in La 2/3-x Li 3x TiO 3 In (a): x is more than 0.05 and less than 0.167.
2. The lithium battery positive electrode structure as set forth in claim 1, wherein: the thickness of the transition layer is 50-100nm, and the thickness of the modification layer is 10-60nm.
3. The preparation method of the positive electrode structure of the lithium battery comprises the following steps:
forming a positive electrode film layer on the positive electrode current collector by using a magnetron sputtering method;
sequentially forming a transition layer and a modification layer on one side, far away from the positive current collector, of the positive film layer by utilizing a magnetron sputtering method, wherein the transition layer comprises a positive electrode material and a fast ion conductor which are contained in the positive film layer, and the modification layer comprises a fast ion conductor;
the transition layer is sputtered together by a lithium cobalt oxide target and a fast ion conductor target so as to be formed on the positive electrode film layer; the modification layer is formed on the transition layer by performing annealing treatment after being sputtered by a fast ion conductor target material singly;
the fast ion conductor is Li 1+y A y Ti 2-x-y M x (PO 4 ) 3 、La 2/3-x Li 3x TiO 3 Any one of them; wherein in Li 1+ y A y Ti 2-x-y M x (PO 4 ) 3 In (a): x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, x+y is more than or equal to 0 and less than or equal to 2, and A is any one of Al, ga, in, sc, Y; m is one of Ge, zr and Hf; in La 2/3-x Li 3x TiO 3 In (a): x is more than 0.05 and less than 0.167.
4. The method for preparing a positive electrode structure of a lithium battery according to claim 3, wherein: the step of forming a positive electrode thin film layer on a positive electrode current collector by using a magnetron sputtering method specifically comprises the following steps:
providing a positive electrode current collector as a substrate;
installing an anode film layer target material;
vacuum was applied to 5 x 10 -4 Pa or less;
heating the substrate holder to a temperature of 100-400 ℃;
and (3) regulating the air pressure to be 0.5-1.5Pa, the ratio of argon to oxygen to be 7:3-9:1, and the sputtering power to be 80-120W, and sputtering for 2 hours to obtain the positive electrode film layer formed on the positive electrode current collector.
5. The method for preparing the positive electrode structure of the lithium battery according to claim 4, wherein: the sputtering power was 120W.
6. The method for preparing a positive electrode structure of a lithium battery according to claim 3, wherein: the transition layer and the modification layer are formed on the positive electrode film layer by utilizing a magnetron sputtering method, and the method comprises the following specific steps:
mounting lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 A target material; mounting a positive electrode thin film layer formed on a positive electrode current collector on a substrate holder;
vacuum was applied to 5 x 10 -4 Pa or less;
heating the substrate holder to a temperature of 100-400 ℃;
the sputtering is carried out by adjusting the air pressure to be 0.5 Pa to 1.0Pa, the ratio of argon to oxygen to be 7:3 to 9:1 and the sputtering power to be 80W to 120W;
lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 Sputtering the target materials together for 30min to obtain a transition layer formed on the positive electrode film layer;
fast ion conductor Li 0.33 La 0.56 TiO 3 Sputtering the target material for 30min independently;
and annealing at 400 ℃ for 3 hours to obtain the modification layer formed on the transition layer.
7. The method for preparing the positive electrode structure of the lithium battery according to claim 6, wherein: lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 Lithium cobalt oxide (LiCoO) during co-sputtering of targets 2 ) Sputtering power of the target material is 120W, and the fast ion conductor Li 0.33 La 0.56 TiO 3 The sputtering power of the target is as follows: 100W; fast ion conductor Li 0.33 La 0.56 TiO 3 The sputtering power of the target material for sputtering alone for 30min is 100W.
8. The method for preparing the positive electrode structure of the lithium battery according to claim 6, wherein: lithium cobalt oxide (LiCoO) 2 ) Target material and fast ion conductor Li 0.33 La 0.56 TiO 3 In the process of co-sputtering target materialThe ratio of argon to oxygen is changed according to the following gradient, and the ratio is as follows: under argon: oxygen=9:1, 8:2, and 7:3 for 10 minutes each.
9. A lithium battery structure, characterized in that: a positive electrode structure comprising the lithium battery as claimed in any one of claims 1-2, a negative electrode structure disposed opposite to the positive electrode structure, and an electrolyte layer between the positive electrode structure and the negative electrode structure.
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