CN114267876A - Integrated electrode-electrolyte structure, preparation method thereof and all-solid-state battery - Google Patents
Integrated electrode-electrolyte structure, preparation method thereof and all-solid-state battery Download PDFInfo
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Abstract
The invention relates to the technical field of batteries, in particular to an integrated electrode-electrolyte structure, a preparation method thereof and an all-solid-state battery. The method comprises the following steps: 1) preparing an electrode with a vertical pore channel by an ice template method; 2) providing a polymer electrolyte precursor slurry; 3) and (3) injecting the polymer electrolyte precursor slurry obtained in the step 2) into the vertical pore channel of the electrode obtained in the step 1) and overflowing on the surface of the electrode, and curing the polymer electrolyte precursor slurry by adopting an in-situ photopolymerization method to prepare and obtain an integrated electrode-electrolyte structure. The invention ensures that the electrode and the electrolyte form good interface contact, and is applied to solid-state batteries at room temperature and 3mg/cm2The electrode has outstanding specific capacity and cycling stability under active load, and the vertical electrode structure is beneficial to improving the diffusion of lithium ions.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an integrated electrode-electrolyte structure, a preparation method thereof and an all-solid-state battery.
Background
Lithium ion batteries are widely used in people's daily life. Solid-state lithium batteries are receiving much attention because of their ability to avoid the drawbacks of flammability, poor thermal stability, leakage of electrolyte, etc. of liquid-state lithium batteries. However, in solid-state lithium batteries, interfacial contact between the positive electrode and the electrolyte is an urgent problem to be solved. Especially in the case of a high active load of the positive electrode, the interfacial contact between the positive electrode material and the electrolyte is insufficient, and these problems have hindered the further development of solid-state lithium batteries.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide an integrated electrode-electrolyte structure, a method of manufacturing the same, and an all-solid battery, which solve the problems of the prior art.
To achieve the above and other related objects, a first aspect of the present invention provides the method comprising the steps of:
1) preparing an electrode with a vertical pore channel by an ice template method;
2) providing a polymer electrolyte precursor slurry;
3) and (3) injecting the polymer electrolyte precursor slurry obtained in the step 2) into the vertical pore channel of the electrode obtained in the step 1) and overflowing on the surface of the electrode, and curing the polymer electrolyte precursor slurry by adopting an in-situ photopolymerization method to prepare and obtain an integrated electrode-electrolyte structure.
In some embodiments of the present invention, the step 1) of preparing the electrode with vertical channels by using an ice template method comprises the following specific steps: electrode materials, conductive agents and binders are dispersed in water and then coated on a current collector, and ice crystals are vertically grown in a low-temperature freezing medium to form a structure having a vertical arrangement, and after sublimation, the ice crystals are provided with vertical pores.
In some embodiments of the invention, the electrode material is selected from lithium iron phosphate, lithium cobaltate, LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.3Mn0.2O2One or more of the above.
In some embodiments of the invention, the conductive agent is selected from the group consisting of conductive carbon black (Super P), acetylene black, superconducting carbon black, and combinations of one or more thereof.
In some embodiments of the invention, the binder is selected from sodium carboxymethylcellulose.
In some embodiments of the invention, the current collector is selected from the group consisting of positive current collectors; preferably, the positive electrode current collector is selected from aluminum foil and/or carbon-containing aluminum foil.
In some embodiments of the invention, the mass ratio of the electrode material, the conductive agent and the binder is (5-10): (0.5-3): 1.
in some embodiments of the invention, the cryogenic freezing medium is selected from liquid nitrogen.
In some embodiments of the present invention, the method of preparing the polymer electrolyte precursor slurry comprises: the polymer electrolyte, the polymer electrolyte additive and the initiator are mixed to provide a polymer electrolyte precursor slurry.
In some embodiments of the invention, the polymer electrolyte is selected from the group consisting of polyethylene glycol diacrylate, epoxy acrylate resins, and combinations of one or more thereof.
In some embodiments of the invention, the polymer electrolyte additive comprises a lithium salt and succinonitrile; the lithium salt is selected from lithium bistrifluoromethanesulfonylimide.
In some embodiments of the invention, the initiator is selected from the group consisting of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and combinations of one or more thereof.
In some embodiments of the invention, the mass ratio of the polymer electrolyte to the polymer electrolyte additive is 1.5: 1 to 3.
In some embodiments of the invention, the mass ratio of the polymer electrolyte to the initiator is 1.5: 0.005-0.03.
In some embodiments of the present invention, in step 3), the in-situ photopolymerization method uses ultraviolet light to perform in-situ curing, and the curing conditions include: the light wavelength of the photocuring is 350-400 nm.
In another aspect, the present invention provides an integrated electrode-electrolyte structure, which is prepared by the method for preparing the integrated electrode-electrolyte structure according to the first aspect of the present invention.
In some embodiments of the present invention, the integrated electrode-electrolyte structure comprises an electrode having a vertical porous structure, a first polymer electrolyte layer filled in the vertical porous structure of the electrode, and a second polymer electrolyte layer provided on the surface of the electrode and the first polymer electrolyte layer, wherein the thickness of the second polymer electrolyte layer is 5 to 20 μm.
In another aspect, the present invention provides an all-solid battery comprising an integrated electrode-electrolyte structure according to the first aspect of the present invention and a negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the anode material with the vertical channel is prepared by using an ice template method, the polymer electrolyte precursor slurry is poured into the vertical channel, the electrolyte is prepared by curing by using an in-situ photopolymerization method, so that good interface contact is formed between the electrode and the electrolyte, and the thickness of the electrolyte is about 5-20 microns. The prepared solid-state battery was at room temperature and 3mg/cm2The electrode has outstanding specific capacity and cycling stability under active load, and the vertical electrode structure is beneficial to improving the diffusion of lithium ions.
Drawings
Fig. 1 shows two types of electrode and electrolyte combination diagrams, in which fig. 1(a) is an electrode having vertical channels prepared using an ice template method and fig. 1(b) is an electrode in which a vertical structure is not formed.
In fig. 2, fig. 2(a) is a view illustrating a process of preparing an electrode having a vertical structure using an ice template. Panel (b) is a top view of an ice template fabricated electrode and the corresponding elemental distribution map (e-h). FIGS. 2(c) and (d) cross-sectional views of an electrode prepared by an ice template before and after the electrode is impregnated with a polymer electrolyte.
In fig. 3, fig. 3(a) impedance spectra of uv-cured polymer electrolytes at different temperatures; FIG. 3(b) is a graph of temperature versus ionic conductivity for a UV cured polymer electrolyte; fig. 3(c) is a linear voltammogram of the uv-cured polymer electrolyte. Fig. 3(d) impedance spectra and fig. 3(e) charge and discharge cycles of symmetric cells assembled using uv-cured polymer electrolytes at room temperature.
In fig. 4, (a) impedance spectra, (b) fitting of diffusion coefficients, (c) first charge and discharge curves, (d) rate performance comparison, and (e) long cycle curves of solid-state batteries prepared with and without electrodes of vertical structure at room temperature.
In fig. 5, fig. 5(a) is shown in conjunction with the flexibility of the electrodes in a vertical configuration and the electrolyte polymerized in situ. (b) And the voltage of the soft package battery is changed in the three-time nailing experiment. (c) And under different damage conditions, the soft package battery lights up the LED lamp for display.
Detailed Description
The following detailed description specifically discloses an integrated electrode-electrolyte structure, a method of making the same, and embodiments of an all-solid-state battery.
The "ranges" disclosed herein are defined in terms of lower limits and upper limits, with a given range being defined by a selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 6-12 and 8-11 are listed for a particular parameter, it is understood that ranges of 6-11 and 8-12 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise stated, the numerical range "x-y" represents a shorthand representation of any combination of real numbers between x and y, where x and y are both real numbers. For example, a numerical range of "0-3" indicates that all real numbers between "0-3" have been listed herein, and "0-3" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (1) and (2), which means that the method can comprise steps (1) and (2) which are performed sequentially, and can also comprise steps (2) and (1) which are performed sequentially. For example, the mention that the process may further comprise step (3) means that step (3) may be added to the process in any order, for example, the process may comprise steps (1), (2) and (3), may also comprise steps (1), (3) and (2), may also comprise steps (3), (2) and (1), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In a first aspect the present invention provides an integrated electrode electrolyte, the method comprising the steps of:
1) preparing an electrode with a vertical pore channel by an ice template method;
2) providing a polymer electrolyte precursor slurry;
3) and (3) injecting the polymer electrolyte precursor slurry obtained in the step 2) into the vertical pore channel of the electrode obtained in the step 1) and overflowing on the surface of the electrode, and curing the polymer electrolyte precursor slurry by adopting an in-situ photopolymerization method to prepare and obtain an integrated electrode-electrolyte structure.
In the integrated electrode electrolyte provided by the invention, the electrode with the vertical pore channel is prepared and obtained by an ice template method in the step 1). The method for preparing the electrode with the vertical pore channel by the ice template method comprises the following specific steps of: electrode materials, conductive agents and binders are dispersed in a solvent and then coated on a current collector, and ice crystals are vertically grown in a low-temperature freezing medium to form a structure having a vertical arrangement, and after sublimation, the ice crystals are provided with vertical channels.
The electrode material is a positive electrode material in step 1), and in some embodiments, the positive electrode material may be a positive electrode material for a battery, which is well known in the art. In some embodiments, the positive electrode material may include at least one of the following materials: lithium iron phosphate, lithium cobaltate, LiNi0.8Co0.1Mn0.1O2(abbreviated as NCM811) and LiNi0.5Co0.3Mn0.2O2(abbreviated as NCM532), and the like.
Step 1) of the present invention, in some embodiments, the conductive agent is selected from one or more of conductive carbon black (Super P), acetylene black, and superconducting carbon black.
Step 1) of the present invention, in some embodiments, the binder is selected from sodium carboxymethylcellulose (CMC for short).
In step 1), the current collector is a positive current collector, and in some embodiments, the positive current collector may be a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may be, for example, a carbon-containing aluminum foil or the like.
Step 1) of the invention, in some embodiments, the mass ratio of the electrode material, the conductive agent and the binder is (5-10): (0.5-3): 1. in some embodiments, the mass ratio of the electrode material, the conductive agent and the binder can be (5-8) to (0.5-3): 1; (8-10) 0.5-3): 1; (5-10) 0.5-1): 1; (5-10) the following (1-2): 1; or (5-10) and (2-3): 1, etc.
In the step 1), the low-temperature freezing medium is liquid nitrogen and the like.
In one embodiment, the electrode material, conductive agent and binder are dispersed in water, then coated on an aluminum foil, which is then placed on liquid nitrogen to form a bottom-up temperature gradient, ice grows from the bottom, pushing the particles together to form a vertically aligned structure. After the ice crystals are frozen, dried and sublimated, namely the ice template is removed, the electrode with the vertical pore channel is formed.
In the integrated electrode electrolyte provided by the invention, step 2) is to provide polymer electrolyte precursor slurry. The preparation method of the polymer electrolyte precursor slurry comprises the following steps: the polymer electrolyte, the polymer electrolyte additive and the initiator are mixed to provide a polymer electrolyte precursor slurry.
In step 2) of the present invention, in some embodiments, the polymer electrolyte is selected from one or more of polyethylene glycol diacrylate and epoxy acrylate resin.
In step 2) of the present invention, the polymer electrolyte additive comprises a lithium salt and succinonitrile. In some embodiments, the lithium salt is selected from lithium bistrifluoromethanesulfonylimide.
In step 2) of the present invention, the initiator is selected from one or more of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and epoxy acrylate resin.
In step 2) of the present invention, the mass ratio of the polymer electrolyte to the polymer electrolyte additive is 1.5: 1 to 3. In some embodiments, the mass ratio of polymer electrolyte to polymer electrolyte additive may also be 1.5: 1-2; or 1.5: 2-3, etc.
In step 2) of the present invention, the mass ratio of the polymer electrolyte to the initiator is 1.5: 0.005-0.03. In some embodiments, the mass ratio of polymer electrolyte to initiator may be 1.5: 0.005-0.01, 1.5: 0.01-0.02, or 1.5: 0.02-0.03, etc.
In the step 2), the mass ratio of the lithium salt to the succinonitrile is 1-2: 1. in some embodiments, the mass ratio of the lithium salt to succinonitrile may be 1 to 1.5: 1. or 1.5 to 2: 1, etc.
In the integrated electrode electrolyte provided by the invention, step 3) is to inject the polymer electrolyte precursor slurry in step 2) into the vertical pore channel of the electrode in step 1) and overflow the surface of the electrode, and an in-situ photopolymerization method is adopted to solidify the polymer electrolyte precursor slurry to prepare and obtain the integrated electrode-electrolyte structure.
In step 3), except for filling all the vertical channels of the electrode, the polymer electrolyte precursor slurry overflows from the surface of the electrode to form a certain thickness, namely the polymer electrolyte layer.
In step 3), the in-situ photopolymerization method adopts ultraviolet light to perform in-situ curing, and the curing conditions include: the light wavelength of the photocuring is 350-400 nm. In some embodiments, the light curing condition may be 350-380nm, 380-400nm, or the like.
In a second aspect, the present invention provides an integrated electrode-electrolyte structure, which is prepared by the method for preparing the integrated electrode-electrolyte structure according to the first aspect of the present invention.
In the integrated electrode-electrolyte structure provided by the invention, the integrated electrode-electrolyte structure comprises an electrode with a vertical porous structure, a first polymer electrolyte layer filled in the vertical porous structure of the electrode, and a second polymer electrolyte layer arranged on the surfaces of the electrode and the first polymer electrolyte layer. Typically, the first polymer electrolyte layer is obtained after curing by in situ photopolymerization by injection into the vertical channels of the electrode by the process of the first aspect of the invention. And a second polymer electrolyte layer formed after the electrode surface has overflowed.
In the integrated electrode-electrolyte structure provided by the invention, the thickness of the second polymer electrolyte layer is 5-20 μm. In some embodiments, the thickness of the second polymer electrolyte layer may be, for example, 5 to 10 μm, 10 to 15 μm, or 15 to 20 μm.
An all-solid-state battery comprising the integrated electrode-electrolyte structure according to the second aspect of the invention and a negative electrode.
In the all-solid-state battery provided by the invention, the material of the negative electrode can be, for example, metallic lithium, graphite, lithium titanate and the like.
The invention has the beneficial effects that:
the invention uses the ice template method to prepare the anode material with the vertical channel, the polymer electrolyte precursor slurry is poured into the vertical channel, the in-situ photopolymerization method is used for curing to prepare the electrolyte, so that the electrodes and the electrolyte are arrangedGood interface contact is formed between the two electrodes, and the thickness of the electrolyte is about 5-20 microns. The prepared solid-state battery was at room temperature and 3mg/cm2The electrode has outstanding specific capacity and cycling stability under active load, and the vertical electrode structure is beneficial to improving the diffusion of lithium ions.
The following examples are provided to further illustrate the advantageous effects of the present invention.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail below with reference to examples. However, it should be understood that the embodiments of the present invention are only for explaining the present invention and are not for limiting the present invention, and the embodiments of the present invention are not limited to the embodiments given in the specification. The examples were prepared under conventional conditions or conditions recommended by the material suppliers without specifying specific experimental conditions or operating conditions.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Polyethylene glycol diacrylate was purchased from aladdin (alatin Mv ≈ 1000).
Example 1:
1.5g of polyethylene glycol diacrylate (PEGDA), 1.4g of lithium bistrifluoromethanesulfonylimide (LITFSI), 1g of succinonitrile and 0.015g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide were mixed uniformly to form a polymer electrolyte precursor.
Coating the electrolyte precursor on polytetrafluoroethylene, and curing under the condition of using ultraviolet light (the light wavelength is 350-400nm) at room temperature to prepare the polymer electrolyte. The ionic conductivity at room temperature was measured to be 1.80X 10-4S cm-1。
The method for testing and calculating the ionic conductivity comprises the following steps: where σ denotes ion conductivity, L denotes a thickness of the electrolyte, R denotes resistance, and S denotes an area.
The impedance spectra at different temperatures are shown in fig. 3, and it can be seen from fig. 3a that the impedance of the electrolyte gradually decreases as the temperature increases.
The temperature and ionic conductivity are plotted in fig. 3b, and from fig. 3b, it can be concluded that the activation energy of the electrolyte is 0.042 ± 0.001 eV.
Linear voltammogram as in fig. 3c, from which it can be seen that the oxidative decomposition voltage of the electrolyte is 4.5V;
the polymer electrolyte solidified by ultraviolet light and metallic lithium are assembled into a symmetrical battery, the impedance spectrum at room temperature is shown in figure 3d, and better interface contact between the electrolyte and a lithium sheet can be seen from figure 3 d; the charge and discharge cycle is shown in fig. 3e, and it can be seen from fig. 3e that no short circuit occurs after 1000h of cycle in the symmetrical cell.
Example 2
1.475g of polyethylene glycol diacrylate (PEGDA), 0.7g of lithium bistrifluoromethanesulfonylimide (LITFSI), 1g of succinonitrile and 0.015g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide were mixed uniformly to form a polymer electrolyte precursor. Coating the electrolyte precursor on polytetrafluoroethylene, and curing under the condition of using ultraviolet light (the light wavelength is 350-400nm) at room temperature to prepare the polymer electrolyte. The ionic conductivity at room temperature was measured to be 1.34X 10-4S cm-1. The ionic conductivity test and calculation method are the same as before.
Example 3:
0.8g of lithium iron phosphate electrode material, 0.1g of conductive carbon black and 0.1g of binder carboxymethylcellulose sodium are dispersed in water, then coated on an aluminum foil, the aluminum foil is placed on liquid nitrogen to form a temperature gradient from bottom to top, ice starts to grow from the bottom, and particles are pushed together to form a vertically arranged structure. After ice freeze-drying sublimation, vertically arranged channels are formed for rapid ion transport. And (3) pouring the polymer electrolyte precursor into a vertical channel, and finally curing by ultraviolet light (the light wavelength is 350-400nm) to form an integrated electrode and electrolyte.
Half-cells were assembled with metallic lithium as the negative electrode at room temperature and 0.1C (1C 170mAh g)-1) The specific capacity of the first discharge measured under the current is 154.3mAh g-1。
The first discharge specific capacity test and calculation method comprises the following steps: specific discharge capacity is discharge capacity per electrode active material.
Comparative example 1
0.8g of lithium iron phosphate electrode material, 0.1g of conductive carbon black and 0.1g of binder are dispersed in N-methylpyrrolidone, then coated on an aluminum foil, and the aluminum foil is placed in a vacuum drying oven and dried overnight at 100 ℃.
The impedance spectrum of the solid-state battery prepared by the electrode having the vertical structure of example 3 and the electrode having no vertical structure of comparative example 1 at room temperature is shown in fig. 4a, and it can be seen from fig. 4a that the electrode material prepared using the ice template has good interfacial contact with the electrolyte.
Fitting test of diffusion coefficients at room temperature for the solid-state battery prepared with the electrode of example 3 having a vertical structure and the electrode of comparative example 1 having no vertical structure as shown in fig. 4b, it can be seen from fig. 4b that the battery prepared using the ice template has a higher diffusion coefficient.
The first charge and discharge curves of the solid-state battery prepared by the electrode of example 3 having a vertical structure and the electrode of comparative example 1 having no vertical structure at room temperature are shown in fig. 4c, and it can be seen from fig. 4c that the battery prepared using the ice template has a higher specific discharge capacity.
Rate performance at room temperature for solid-state batteries prepared with the electrode of example 3 having a vertical structure and the electrode of comparative example 1 having no vertical structure as compared to fig. 4d, it can be seen from fig. 4d that the battery prepared using the ice template has better rate performance.
The long cycling curves at room temperature for solid-state batteries prepared with the electrode of example 3 having a vertical structure and the electrode of comparative example 1 without a vertical structure are shown, for example, in fig. 4e, from which it can be seen that the batteries prepared using the ice template have more stable cycling performance.
Figure 5a is a display of the flexibility of an electrode and an in situ polymerized electrolyte in combination with a vertical structure. It can be seen from fig. 5a that the integrated electrode-electrolyte structure has good flexibility.
Figure 5b pouch cell voltage change in three nail penetration experiments. It can be seen from fig. 5b that the pouch battery has an excellent advantage of preventing combustion and explosion.
Fig. 5c shows that the pouch cell lights up the LED lamp under different failure conditions (bending, clipping once, clipping twice), and it can be seen from fig. 5c that the pouch cell has high safety.
Example 4
1g of lithium iron phosphate electrode material, 0.1g of conductive carbon black and 0.1g of binder carboxymethylcellulose sodium are dispersed in water, then coated on an aluminum foil, the aluminum foil is placed on liquid nitrogen to form a temperature gradient from bottom to top, ice starts to grow from the bottom, and particles are pushed together to form a vertically-arranged structure. After sublimation of the ice (freeze-drying), vertically aligned channels are formed for rapid ion transport. And (3) pouring the polymer electrolyte precursor into a vertical channel, and finally curing by ultraviolet light (the light wavelength is 350-400nm) to form an integrated electrode and electrolyte.
Half-cells were assembled with metallic lithium as the negative electrode at room temperature and 0.1C (1C 170mAh g)-1) The specific capacity of the first discharge measured under the current is 148.6mAh g-1。
The first discharge specific capacity test and calculation method comprises the following steps: specific discharge capacity is discharge capacity per electrode active material.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (10)
1. A method of making an integrated electrode-electrolyte structure, the method comprising the steps of:
1) preparing an electrode with a vertical pore channel by an ice template method;
2) providing a polymer electrolyte precursor slurry;
3) and (3) injecting the polymer electrolyte precursor slurry obtained in the step 2) into the vertical pore channel of the electrode obtained in the step 1) and overflowing on the surface of the electrode, and curing the polymer electrolyte precursor slurry by adopting an in-situ photopolymerization method to prepare and obtain an integrated electrode-electrolyte structure.
2. The method for preparing an integrated electrode-electrolyte structure according to claim 1, wherein the step 1) of preparing the electrode with vertical channels by an ice template method comprises the following specific steps: electrode materials, conductive agents and binders are dispersed in water and then coated on a current collector, and ice crystals are vertically grown in a low-temperature freezing medium to form a structure having a vertical arrangement, and after sublimation, the ice crystals are provided with vertical pores.
3. The method of making an integrated electrode-electrolyte structure of claim 2, further comprising any one or more of the following conditions:
A1) the electrode material is selected from lithium iron phosphate, lithium cobaltate and LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.3Mn0.2O2One or more combinations of;
A2) the conductive agent is selected from one or more of conductive carbon black (Super P), acetylene black and superconducting carbon black;
A3) the binder is selected from sodium carboxymethyl cellulose;
A5) the current collector is selected from a positive current collector; preferably, the positive electrode current collector is selected from aluminum foil and/or carbon-containing aluminum foil;
A6) the mass ratio of the electrode material to the conductive agent to the binder is (5-10) to (0.5-3): 1;
A7) the cryogenic freezing medium is selected from liquid nitrogen.
4. The method of making an integrated electrode-electrolyte structure according to claim 1, wherein the method of making the polymer electrolyte precursor slurry comprises: the polymer electrolyte, the polymer electrolyte additive and the initiator are mixed to provide a polymer electrolyte precursor slurry.
5. The method of making an integrated electrode-electrolyte structure of claim 4, further comprising any one or more of the following conditions:
B1) the polymer electrolyte is selected from one or more of polyethylene glycol diacrylate and epoxy acrylate resin;
B2) the polymer electrolyte additive includes a lithium salt and succinonitrile; the lithium salt is selected from lithium bistrifluoromethanesulfonylimide;
B3) the initiator is selected from one or more of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone.
6. The method of making an integrated electrode-electrolyte structure of claim 4, further comprising any one or more of the following conditions:
C1) the mass ratio of the polymer electrolyte to the polymer electrolyte additive is 1.5: 1-3;
C2) the mass ratio of the polymer electrolyte to the initiator is 1.5: 0.005-0.03.
7. The method for preparing the integrated electrode-electrolyte structure according to claim 1, wherein in step 3), the in-situ photopolymerization method is used for in-situ curing by using ultraviolet light, and the curing conditions comprise: the light wavelength of the photocuring is 350-400 nm.
8. An integrated electrode-electrolyte structure prepared by the method for preparing the integrated electrode-electrolyte structure according to any one of claims 1 to 7.
9. The integrated electrode-electrolyte structure of claim 8, wherein the integrated electrode-electrolyte structure comprises a vertically porous structure of the electrode, a first polymer electrolyte layer filled in the vertically porous structure of the electrode, and a second polymer electrolyte layer provided on the surface of the electrode and the first polymer electrolyte layer, and the thickness of the second polymer electrolyte layer is 5 to 20 μm.
10. An all-solid battery comprising the integrated electrode-electrolyte structure of claim 8 and a negative electrode.
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