CN110061287A - A kind of solid union dielectric film and its preparation and application - Google Patents

A kind of solid union dielectric film and its preparation and application Download PDF

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CN110061287A
CN110061287A CN201810049439.1A CN201810049439A CN110061287A CN 110061287 A CN110061287 A CN 110061287A CN 201810049439 A CN201810049439 A CN 201810049439A CN 110061287 A CN110061287 A CN 110061287A
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electrolyte
solid
lithium
peo
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CN110061287B (en
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范坤
庞自钊
魏贝贝
李化一
于书达
高月
沙金
苏迎春
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Tianjin Guoan MGL New Materials Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
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Abstract

The present invention relates to a kind of solid union dielectric film and its preparation and application, the solid union dielectric film includes inorganic solid electrolyte, organic bath and polymer dielectric, and preparation is by inorganic solid electrolyte Li1+xAlxTi2–x(PO4)3(wherein, 0 < x < 1), organic bath and polymer dielectric polyoxyethylene (PEO) are mixed according to a certain percentage.The solid union dielectric film that the present invention is prepared is Inorganic whisker dielectric film, it is preferred for the electrolyte of all-solid lithium-ion battery, solid union dielectric film of the invention not only mechanical strength with higher, electric conductivity is good, and make deposition and abjection of the lithium on lithium metal more uniform, the generation that can stop Li dendrite well, the battery discharge specific capacity height prepared with the dielectric film, good rate capability.

Description

Solid composite electrolyte membrane and preparation and application thereof
Technical Field
The invention belongs to the field of electrolyte materials of lithium ion secondary batteries, and particularly relates to an all-solid-state lithium ion battery electrolyte with good mechanical property and conductivity, and preparation and application thereof.
Background
As a novel green secondary battery, the all-solid-state lithium ion battery has the advantages of small volume, light weight, long cycle life, small self-discharge, no memory effect and the like, and is widely applied. In recent years, with the rapid development of mobile phones and notebook computers and the demand of electric and hybrid vehicles, higher requirements are made on the energy density and safety performance of batteries. Electrolytes play an important role in lithium ion batteries as a medium for lithium ion conduction between the positive and negative electrodes. In recent years, researchers have been expecting to improve the performance of lithium ion batteries from the aspect of positive and negative electrode materials, and few attempts have been made to improve the performance of the batteries by using a novel electrolyte.
In a conventional lithium ion battery, an electrolyte is composed of a small-molecular lithium salt of lithium ions and a solvent. LiPF6The excellent electrochemical performance of EC/DMC is considered as the standard of electrolyte in lithium ion battery, and is the leading of commercial electrolyte at present. But the defects are also not negligible, and the problems of flammability, easy leakage, formation of lithium ion dendrite and SEI film and the like are solved. Currently, lithium ion battery accidents occur frequently, and most of the catastrophic battery accidents begin with the burning of the electrolyte. Therefore, lithium ion batteries with higher safety performance, represented by all-solid batteries, are the hot spot of research today. The next generation lithium battery of electric vehicles and mobile phones will select all solid state lithium ion batteries with higher energy density and better safety. With conventional LiPF6The solid electrolyte can suppress the generation of lithium dendrites during battery operation and reduce the possibility of short circuits, compared to EC/DMC electrolytes.
Solid electrolytes are mainly classified into inorganic solid electrolytes, solid polymer electrolytes, and composite solid electrolytes. The traditional solid polymer electrolyte has low normal-temperature conductivity and narrow electrochemical window. The inorganic solid electrolyte is poor in flexibility and has a large interface resistance. As the combination of the two, the composite solid electrolyte not only has flexibility, but also has good conductivity at relatively low temperature, and has wide research prospect.
Therefore, a solid-state composite lithium ion battery electrolyte membrane with good mechanical properties and good conductivity and a preparation method thereof are needed to meet the market and industrialization requirements.
Disclosure of Invention
To solve the above problems, the present inventionThe inventor carries out intensive research and finds that: mixing inorganic solid electrolyte Li1+ xAlxTi2–x(PO4)3The (LATP), the organic electrolyte and the polymer electrolyte Polyoxyethylene (PEO) are mixed according to a certain proportion, wherein x is more than 0 and less than 1, and the inorganic-organic composite solid electrolyte membrane is prepared. The solid composite electrolyte membrane prepared by the invention not only has higher mechanical strength and good conductivity, but also ensures that the deposition and the separation of lithium on the metal lithium are more uniform, can well prevent the generation of lithium dendrite, and has high discharge specific capacity of the battery prepared by the electrolyte membrane. The preparation method has simple conditions and low requirements on production equipment, thereby completing the invention.
The object of the present invention is to provide the following:
(1) a solid composite electrolyte membrane is composed of an inorganic solid electrolyte, an organic electrolyte and a polymer electrolyte, wherein the inorganic solid electrolyte is Li1+xAlxTi2–x(PO4)3(LATP), wherein 0 < x < 1, preferably x is 0.3; the organic electrolyte is organic lithium boron salt; the polymer electrolyte is polyoxyethylene PEO, polyvinylidene fluoride PVDF, polyacrylonitrile PAN, preferably PEO, and more preferably PEO with a molecular weight of 105～107Still more preferably, it has a molecular weight of 106。
(2) A method for producing a solid composite electrolyte membrane, comprising the steps of:
step 1, preparing inorganic solid electrolyte Li through solid-state reaction1+xAlxTi2–x(PO4)3(LATP), wherein 0 < x < 1;
step 2, preparing an organic electrolyte;
and 3, mixing and stirring the product obtained in the step 1, the product obtained in the step 2 and the polymer electrolyte in a solvent, coating, removing the solvent, and drying in vacuum to obtain a final product.
(3) The use of the solid composite electrolyte membrane according to (1),
the electrolyte is used for the electrolyte of a solid lithium ion battery, and preferably, the solid lithium ion battery prepared by using the electrolyte has the specific discharge capacity of 158.9mAh/g at the temperature of 60 ℃ under 0.1C; the specific discharge capacity of 95mAh/g is obtained under the multiplying power of 2C.
According to the solid composite electrolyte membrane and the preparation and the application thereof provided by the invention, the following beneficial effects are achieved:
1) each component of the solid composite electrolyte membrane provided by the invention plays its own role and is effectively synergistic; the inorganic solid electrolyte provides a lithium ion channel, and the composite solid electrolyte membrane has better mechanical property; the macromolecular polymer PEO not only can conduct lithium ions, but also plays a role of a binder, namely, the LATP ceramic particles are bonded; the organic electrolyte firstly reduces the crystallinity of PEO and secondly softens the contact between solid-solid interfaces, so that the deposition and the desorption of lithium on the metal lithium can be more uniform, and the electrolyte can well block the generation of lithium dendrite;
2) the battery prepared by the solid composite electrolyte membrane has the specific discharge capacity of 158.9mAh/g at 0.1C under the condition of 60 ℃ within the range of 2.5V-3.9V; the discharge specific capacity of 95mAh/g is obtained under the 2C multiplying power;
3) the preparation method of the solid composite electrolyte membrane provided by the invention has the advantages of simple process, low price of the used solvent, low requirement on the used production equipment, easiness in operation and reduction of cost, and the factors are favorable for industrial popularization.
Drawings
FIG. 1 shows Li in the present invention1.3Al0.3Ti1.7(PO4)3An XRD pattern of (a);
fig. 2 shows cell rate test curves at 60 ℃ for the composite electrolyte membranes prepared in examples and comparative examples.
Fig. 3 shows specific discharge capacity curves of 0.1C at 60C of the composite electrolyte membranes prepared in examples 1 to 5.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The object of the present invention is to provide a solid composite electrolyte membrane composed of an inorganic solid electrolyte composed of the formula Li, an organic electrolyte and a polymer electrolyte1+xAlxTi2–x(PO4)3Wherein 0 < x < 1, preferably x is 0.3;
the organic electrolyte is organic lithium boron salt;
the polymer electrolyte is polyoxyethylene PEO, polyvinylidene fluoride PVDF, polyacrylonitrile PAN, preferably PEO, and more preferably PEO with a molecular weight of 105～107Still more preferably, it has a molecular weight of 106。
The inorganic solid electrolyte Li1+xAlxTi2–x(PO4)3(LATP for short), wherein x is more than 0 and less than 1, is a common NASICON type ceramic solid electrolyte at present, and the solid electrolyte has excellent waterproof performance and lithium ion conduction capability and also has better waterproof performance and lithium ion conduction capability than the conventional solid electrolyteHigh mechanical strength.
However, the inorganic solid electrolyte has the disadvantages of poor flexibility, large interfacial resistance, and difficulty in large-rate charge and discharge.
The polymer solid-state lithium ion battery formed by compounding the polymer electrolyte and the lithium salt has the advantages of high safety, capability of being prepared into various shapes, good contact wettability with an electrode material and the like, but the polymer solid-state lithium battery also has obvious defects, the used polymer electrolyte has high crystallinity at room temperature, very low ionic conductivity and narrow electrochemical stability window, the matched electrode material is limited, and the interface between the polymer solid electrolyte and the electrode is unstable, so that the application of the polymer solid-state lithium ion battery is limited.
The composite solid electrolyte assembled by the inorganic-organic composite electrolyte can effectively combine the performance advantages of inorganic and polymer solid lithium batteries, and accords with the technical development direction of future high-power safe and high-efficiency solid batteries.
The present inventors believe that the organic electrolyte of the present invention, i.e., the organolithium boron salt, enables the crystallinity of PEO (polyoxyethylene) to be reduced, softening the contact between solid-solid interfaces, and thus enabling more uniform deposition and extraction of lithium on the metallic lithium.
The inventor believes that the ionic conductivity of the polymer PEO electrolyte is mainly caused by migration and conduction of lithium salt in an amorphous region of the polymer, a crystalline region contributes less to the ionic conductivity, and the polymer with small crystallinity has higher conductivity because the migration of lithium ions in the polymer electrolyte PEO is mainly in an amorphous region of the polymer;
the inventors have discovered that the polymer electrolyte PEO is not only capable of conducting lithium ions, but also acts as a binder, binding the LATP ceramic particles; but it has the disadvantage that the room temperature conductivity is too low (typically 10)-8On the order of S/cm) and useful ionic conductivity should be 10-4And the S/cm is higher than that of the PEO, so that the composition of the PEO and the inorganic solid electrolyte and the organic lithium boron salt has good application prospect.
The inventor finds that the composite solid electrolyte formed by compounding the inorganic solid electrolyte, the organic electrolyte and the polymer electrolyte PEO has a good synergistic effect, the three components play roles in the composite solid electrolyte, the inorganic solid electrolyte provides a lithium ion channel, and the composite solid electrolyte has high mechanical strength; the polymer electrolyte PEO not only can conduct lithium ions, but also plays a role of a binder and binds LATP ceramic particles; the organic electrolyte firstly reduces the crystallinity of PEO and then softens the contact between solid-solid interfaces, so that the deposition and the separation of lithium on the metal lithium can be more uniform, and the composite solid electrolyte can well block the generation of lithium dendrites by having the characteristics, thereby having better electrical property.
It is another object of the present invention to provide a method for preparing a solid composite electrolyte membrane, comprising the steps of:
step 1, preparing an inorganic solid electrolyte through a solid-state reaction;
in step 1, the inorganic solid electrolyte is made of Li1+xAlxTi2–x(PO4)3Wherein 0 < x < 1, preferably x is 0.3;
the inorganic solid electrolyte LATP is a common NASICON type ceramic solid electrolyte at present, and has excellent waterproof performance, lithium ion conductivity and high mechanical strength.
Step 1 comprises the following substeps:
substep 1-1: weighing inorganic lithium salt, aluminum oxide, titanium oxide and phosphate according to a stoichiometric ratio, and mixing;
substeps 1-2: calcining the system obtained in the substep 1;
substeps 1-3: crushing, sintering, crushing again and drying in vacuum the system obtained in the substep 2 to obtain an inorganic solid electrolyte;
preferably, the first and second electrodes are formed of a metal,
in substep 1-1, the inorganic lithium salt is lithium carbonate or lithium hydroxide, preferably lithium carbonate; the phosphate is ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate, and preferably diammonium hydrogen phosphate;
in the substep 1-2, the calcination temperature is 800-1000 ℃ and the calcination time is 2-3 h;
in the substep 1-3, the crushing is ball milling, the ball milling is carried out by using an organic solvent, the organic solvent is one or more of ethanol, propanol, isopropanol and acetone, preferably acetone, the sintering temperature is 800-1000 ℃, and the sintering time is 2-3 h; and the step of re-crushing is ball milling, the ball milling time is 5-8 h, preferably 6h, the vacuum drying temperature is 80-120 ℃, the vacuum drying temperature is preferably 100 ℃, and the vacuum drying time is 6-8 h.
Ball milling is also known as ball milling, a common apparatus for grinding or milling. The materials are crushed and mixed by the impact of falling grinding bodies (such as steel balls, cobbles, etc.) and the grinding action of the grinding bodies and the inner wall of the ball mill.
The inventor finds that the LATP obtained after ball milling has more uniform particle size and larger specific surface area, so that the prepared electrolyte membrane has better performance.
The inventors have found that, in the inorganic solid-state electrolyte LATP of the present invention, as aluminum ions are doped, in order to maintain charge balance, a corresponding amount of lithium ions must enter into vacancies, and an increase in the amount of lithium ions relatively increases the conductivity of the inorganic solid-state electrolyte LATP, so that an increase in the amount of interstitial lithium ions in a certain range is more favorable for the improvement of conductivity, resulting in an increase in conductivity as the Al content increases, but if the amount of interstitial lithium ions is too large, the amount of unoccupied lithium vacancies is too small to be favorable for the cooperative motion of the interstitial lithium ions, and the conductivity is rather decreased, so that x in the present invention is preferably 0.3.
Step 2, preparing an organic electrolyte;
step 2 comprises the following substeps:
substep 2-1: dropwise adding the lithium borohydride solution into the tetrahalo-p-xylylene alcohol solution, controlling the dropwise adding temperature to be 40-50 ℃, and after the dropwise adding is finished, carrying out reflux reaction;
substep 2-2: cooling after the reaction is finished, and performing post-treatment to obtain a product;
preferably, the first and second electrodes are formed of a metal,
in the substep 2-1, the tetrahalogen terephthalyl alcohol is tetrafluoroterephthalyl alcohol, tetrachloroterephthalyl alcohol, tetrabromophthalyl alcohol, tetraiodo terephthalyl alcohol, preferably tetrachloroterephthalyl alcohol; the solvent for the solution is tetrahydrofuran, and the reflux reaction time is 6-8 h;
the lithium borohydride solution is a 2M lithium borohydride tetrahydrofuran solution; white precipitate was observed to form during the addition. The reaction dropping temperature is preferably 45 ℃. The whole reaction process is carried out under the protection of inert gas.
In the substep 2-2, the post-treatment comprises filtering, washing the filter cake with a solvent, and then vacuum-drying the filter cake at 60-80 ℃ for 24-48h to obtain the organolithium boron salt electrolyte.
In a preferred embodiment, after the reaction is finished, the temperature is naturally reduced to room temperature, the precipitate is filtered, the precipitate is washed with anhydrous tetrahydrofuran, and the washing is repeated for several times. And then drying the filter cake in vacuum to obtain the organic electrolyte white solid.
The inventor believes that one of the most important components in the lithium ion battery is the electrolyte of the lithium ion battery, and the lithium salt is an important component in the electrolyte of the lithium ion battery, and whether the lithium salt is suitable or not determines the performance of the lithium ion battery.
The inventor also thinks that the organic lithium boron salt electrolyte prepared in the invention is formed by combining lithium ions and a large chelating anion taking B as a central ion, oxygen is coordinated with B in the anion, and a ligand and B form large pi conjugation after coordination, so that the negative charge of the central ion is dispersed, the large anion is more stable, the transference number of the lithium ions is higher, and meanwhile, the performance of the organic lithium boron salt electrolyte in the invention is better.
The inventor also believes that the organic electrolyte lithium boron salt prepared by the invention can reduce the crystallinity of PEO (polyethylene oxide), soften the contact between solid and solid interfaces, and enable more uniform deposition and extraction of lithium on the lithium metal.
And 3, mixing the product obtained in the step 1, the product obtained in the step 2 and the polymer electrolyte to prepare the solid composite electrolyte membrane.
In step 3, the polymer electrolyte is polyoxyethylene PEO, polyvinylidene fluoride PVDF, polyacrylonitrile PAN, preferably PEO, and more preferably, the molecular weight of PEO is 105～107Still more preferably, it has a molecular weight of 106。
In step 3, the preparation steps include: placing the inorganic solid electrolyte prepared in the step 1, the product prepared in the step 2 and the polymer electrolyte into a solvent, mixing and stirring uniformly, coating the obtained mixed solution, removing the solvent, and drying in vacuum;
wherein,
the mass ratio of the inorganic solid electrolyte, the organic electrolyte and the polymer electrolyte is 0.8:0.1:0.1, 0.7:0.15:0.15, preferably 0.7:0.15:0.15,
the solvent is NMP or acetonitrile, preferably acetonitrile, and more preferably anhydrous acetonitrile.
The temperature of the solvent removal is 50-100 ℃, preferably 60-80 ℃, such as 70 ℃;
the vacuum drying temperature is 70-120 deg.C, preferably 80-100 deg.C, such as 80 deg.C, and the vacuum drying time is 1-5h, preferably 2-3h, such as 2 h.
The polymer electrolyte of the present invention refers to a polymer matrix in a polymer solid electrolyte (SPE) composed of a polymer matrix (e.g., polyester, polyether, polyamine, etc.) and a lithium salt (e.g., LiClO)4、LiAsF6、LiPF6、LiBF4Etc.) have received wide attention due to their light weight, good viscoelasticity, excellent machinability, etc. Common polymer matrices developed to date include polyethylene oxide (PEO), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polypropylene oxide (PPO), polyvinylidene chloride (PVDC), and uniionic polymer electrolytes, among other systems. Currently, the mainstream SPE matrix is still the earliest PEO and its derivatives proposed, mainly benefiting from the stability of PEO to metallic lithium and the better dissociation of lithium salts. However, because of the high crystallinity of the matrix PEO of the polymer electrolyte, the conductivity of the obtained polymer solid electrolyte compounded by PEO and Li salt is low at room temperature, which limits the application of the polymer solid electrolyte to a certain extent.
The inventor finds that the main aspect influencing the conductivity of a polymer electrolyte matrix PEO is the flexibility of a polymer chain, the crystallinity of PEO is reduced by adding the organic electrolyte lithium boron salt, the contact between solid and solid interfaces is softened, so that the deposition and the desorption of lithium on metal lithium are more uniform, the generation of lithium dendrites can be well blocked, and the solid composite electrolyte membrane has better electrical property.
The invention also provides the application of the composite solid electrolyte membrane, preferably the electrolyte of the solid lithium ion battery, wherein the composite solid electrolyte membrane is used as the electrolyte of the lithium ion battery made of the electrolyte, the specific discharge capacity of the lithium ion battery at 60 ℃ is up to 158.9mAh/g, and the 2.5V-3.9V range is between 0.1C; the specific discharge capacity of 95mAh/g is obtained under the multiplying power of 2C.
Examples
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
Example 1
Weighing 0.0480g of lithium carbonate, 0.0153g of alumina, 0.136g of titanium dioxide and 0.396g of diammonium phosphate according to the stoichiometric ratio, uniformly mixing, and sintering for 2 hours at 900 ℃. Ball milling with acetone as solvent, sintering at 900 deg.c for 2 hr, ball milling for 6 hr, and vacuum drying at 100 deg.c to obtain solid electrolyte Li1.3Al0.3Ti1.7(PO4)3Abbreviated as LATP-1;
2.759g of tetrachloroterephthalyl alcohol is taken, 20mL of anhydrous tetrahydrofuran is added to dissolve the tetrachloroterephthalyl alcohol, and after complete dissolution, 5mmol of 2M LiBH is slowly dropped into the solution4And THF solution, wherein white precipitate is observed to be generated in the process, the reaction temperature is controlled at 45 ℃ in the process of dropwise adding, stirring and refluxing are carried out for 6 hours after the dropwise adding is finished, and the whole reaction process is carried out under the protection of inert gas. Naturally cooling to room temperature after the reaction is finished, filtering out the precipitate, washing a filter cake with anhydrous tetrahydrofuran, and repeating the steps for several times. Finally, drying the product in vacuum for 36h at the temperature of 60 ℃ to obtain a white solid organic electrolyte;
0.7g of LATP-1 in step (1), 0.15g of the white solid organic electrolyte in step (2) and 0.15g of PEO (molecular weight 10) were weighed out6) The mixture is put into anhydrous acetonitrile to be mixed and stirred, the uniformly stirred mixed solution is coated on a glass plate and dried at 70 ℃, and then the glass plate is put into a vacuum oven at 80 ℃ to be dried for 2 hours to prepare a solid composite electrolyte membrane, wherein the serial number of the solid composite electrolyte membrane is LPB-1.
Example 2
Weighing 0.0480g of lithium carbonate, 0.0153g of alumina, 0.136g of titanium dioxide and 0.396g of diammonium phosphate according to the stoichiometric ratio, uniformly mixing, and sintering for 2 hours at 900 ℃. Ball milling with acetone as solvent, sintering at 900 deg.C for 2 hr, ball milling for 6 hr, and finalVacuum drying at 100 ℃ to obtain the inorganic solid electrolyte Li1.3Al0.3Ti1.7(PO4)3Abbreviated as LATP-1;
2.759g of tetrachloroterephthalyl alcohol is taken, 20mL of anhydrous tetrahydrofuran is added to dissolve the tetrachloroterephthalyl alcohol, and after complete dissolution, 5mmol of 2M LiBH is slowly dropped into the solution4And THF solution, wherein white precipitate is observed to be generated in the process, the reaction temperature is controlled at 45 ℃ in the process of dropwise adding, stirring and refluxing are carried out for 6 hours after the dropwise adding is finished, and the whole reaction process is carried out under the protection of inert gas. Naturally cooling to room temperature after the reaction is finished, filtering out the precipitate, washing a filter cake with anhydrous tetrahydrofuran, and repeating the steps for several times. Finally, drying the product in vacuum for 36h at the temperature of 60 ℃ to obtain a white solid organic electrolyte;
0.8g of LATP-1 in step (1), 0.10g of the white solid organic electrolyte in step (2) and 0.10g of PEO (molecular weight 10) were weighed out6) The mixture is put into anhydrous acetonitrile to be mixed and stirred, the uniformly stirred mixed solution is coated on a glass plate and dried at 70 ℃, and then the glass plate is put into a vacuum oven at 80 ℃ to be dried for 2 hours to prepare a solid composite electrolyte membrane, wherein the serial number of the solid composite electrolyte membrane is LPB-2.
Example 3
0.0480g of lithium carbonate, 0.0153g of alumina, 0.136g of titanium dioxide and 0.396g of ammonium dihydrogen phosphate are weighed according to the stoichiometric ratio, uniformly mixed and sintered for 2 hours at 900 ℃. Ball milling with acetone as solvent, sintering at 900 deg.c for 2 hr, ball milling for 6 hr, and vacuum drying at 100 deg.c to obtain solid electrolyte Li1.3Al0.3Ti1.7(PO4)3Abbreviated as LATP-2;
2.759g of tetrachloroterephthalyl alcohol is taken, 20mL of anhydrous tetrahydrofuran is added to dissolve the tetrachloroterephthalyl alcohol, and after complete dissolution, 5mmol of 2M LiBH is slowly dropped into the solution4THF solution, white precipitate formation was observed during the process, the reaction temperature was controlled at 45 ℃ during the dropwise addition, the mixture was stirred and refluxed for 6 hours after the dropwise addition, and the whole reaction process was completedUnder the protection of inert gas. Naturally cooling to room temperature after the reaction is finished, filtering out the precipitate, washing a filter cake with anhydrous tetrahydrofuran, and repeating the steps for several times. Finally, drying the product in vacuum for 36h at the temperature of 60 ℃ to obtain a white solid organic electrolyte;
0.7g of LATP-2 in step (1), 0.15g of the white solid organic electrolyte in step (2) and 0.15g of PEO (molecular weight 10) were weighed out6) The composite electrolyte membrane is placed in an anhydrous acetonitrile solution to be mixed and stirred, the uniformly stirred mixed solution is coated on a glass plate, dried at 70 ℃, and then placed in a vacuum oven at 80 ℃ to be dried for 2 hours, so that a solid composite electrolyte membrane is prepared, and the serial number of the solid composite electrolyte membrane is LPB-3.
Example 4
Weighing 0.0480g of lithium carbonate, 0.0153g of alumina, 0.136g of titanium dioxide and 0.396g of diammonium phosphate according to the stoichiometric ratio, uniformly mixing, and sintering for 2 hours at 900 ℃. Ball milling with acetone as solvent, sintering at 900 deg.c for 2 hr, ball milling for 6 hr, and vacuum drying at 100 deg.c to obtain solid electrolyte Li1.3Al0.3Ti1.7(PO4)3Abbreviated as LATP-1;
2.759g of tetrafluoroterephthalyl alcohol is taken, 20mL of anhydrous tetrahydrofuran is added to dissolve the tetrafluoroterephthalyl alcohol, and after complete dissolution, 5mmol of 2M LiBH is slowly dropped into the solution4And THF solution, wherein white precipitate is observed to be generated in the process, the reaction temperature is controlled at 45 ℃ in the process of dropwise adding, stirring and refluxing are carried out for 6 hours after the dropwise adding is finished, and the whole reaction process is carried out under the protection of inert gas. Naturally cooling to room temperature after the reaction is finished, filtering out the precipitate, washing a filter cake with anhydrous tetrahydrofuran, and repeating the steps for several times. Finally, drying the product in vacuum for 36h at the temperature of 60 ℃ to obtain a white solid organic electrolyte;
0.7g of LATP-1 in step (1), 0.15g of the white solid organic electrolyte in step (2) and 0.15g of PEO (molecular weight 10) were weighed out6) Mixing and stirring the mixture in anhydrous acetonitrile solution, and coating the uniformly stirred mixed solution on a glass plateDrying at 70 ℃, and then drying in a vacuum oven at 80 ℃ for 2h to obtain the solid composite electrolyte membrane, wherein the number of the solid composite electrolyte membrane is LPB-4.
Example 5
Weighing 0.0480g of lithium carbonate, 0.0153g of alumina, 0.136g of titanium dioxide and 0.396g of diammonium phosphate according to the stoichiometric ratio, uniformly mixing, and sintering for 2 hours at 900 ℃. Ball milling with acetone as solvent, sintering at 900 deg.c for 2 hr, ball milling for 6 hr, and vacuum drying at 100 deg.c to obtain solid electrolyte Li1.3Al0.3Ti1.7(PO4)3Abbreviated as LATP-1;
2.759g of tetrachloroterephthalyl alcohol is taken, 20mL of anhydrous tetrahydrofuran is added to dissolve the tetrachloroterephthalyl alcohol, and after complete dissolution, 5mmol of 2M LiBH is slowly dropped into the solution4And THF solution, wherein white precipitate is observed to be generated in the process, the reaction temperature is controlled at 45 ℃ in the process of dropwise adding, stirring and refluxing are carried out for 6 hours after the dropwise adding is finished, and the whole reaction process is carried out under the protection of inert gas. Naturally cooling to room temperature after the reaction is finished, filtering out the precipitate, washing a filter cake with anhydrous tetrahydrofuran, and repeating the steps for several times. Finally, drying the product in vacuum for 36h at the temperature of 60 ℃ to obtain a white solid organic electrolyte;
weighing 0.7g of LATP-1 in the step (1), 0.15g of white solid organic electrolyte in the step (2) and 0.15g of PEO (molecular weight is 50 ten thousand), placing the mixture into an anhydrous acetonitrile solution, mixing and stirring, coating the uniformly stirred mixed solution on a glass plate, drying at 70 ℃, and then placing the glass plate in a vacuum oven at 80 ℃ for drying for 2 hours to prepare a solid composite electrolyte membrane, wherein the serial number of the solid composite electrolyte membrane is LPB-5.
Comparative example
Comparative example 1
Weighing 0.0480g of lithium carbonate, 0.0153g of alumina, 0.136g of titanium dioxide and 0.396g of diammonium phosphate according to the stoichiometric ratio, uniformly mixing, and sintering for 2 hours at 900 ℃. Ball milling with acetone as solvent, sintering at 900 deg.C for 2 hr to obtain ballGrinding for 6h, and finally drying in vacuum at 100 ℃ to obtain the inorganic solid electrolyte Li1.3Al0.3Ti1.7(PO4)3Abbreviated as LATP-1;
0.7g of LATP-1 from step (1) and 0.3g of PEO (molecular weight 10) were weighed6) And placing the mixture in an anhydrous acetonitrile solution for mixing and stirring, coating the uniformly stirred mixed solution on a glass plate, drying at 70 ℃, and then placing the glass plate in a vacuum oven at 80 ℃ for drying for 2 hours to obtain a solid composite electrolyte membrane, wherein the serial number of the solid composite electrolyte membrane is LP.
Examples of the experiments
Experimental example 1 XRD Pattern of LATP
The test method comprises the following steps: the XRD structure of LATP prepared in the present invention was measured by X-ray diffractometry, and the results are shown in FIG. 1.
FIG. 1 is an XRD pattern of LATP-1 and LATP-2 obtained in step 1 of examples 1 and 3 of the present invention. Wherein,
a shows the XRD profile of LATP-1;
b shows a plot of a standard spectrogram (PDF-card);
c shows the XRD profile of LATP-2.
As can be seen from FIG. 1, the structures of LATP-1 and LATP-2 produced by the present invention are consistent with the standard spectrum.
Experimental example 2 measurement of Properties
2.1 preparation of LFP/LPB/Li Battery
Weighing 0.5g of lithium iron phosphate, 0.3g of acetylene black and 0.2g of PEO, mixing the mixture in anhydrous acetonitrile, stirring the mixture for 12 hours, coating the synthesized slurry on an aluminum foil, drying the aluminum foil in a vacuum oven at 80 ℃ for 12 hours, and processing the aluminum foil to obtain the LFP. Then, the solid composite electrolyte membrane LPB prepared by the method is used as an electrolyte to prepare the button cell with the LFP/LPB/Li structure, wherein the composite membrane LPB is the electrolyte and has the property of a diaphragm. All experiments were performed in a glove box.
2.2 preparation of LFP/LP/Li cell
0.5g of lithium iron phosphate, 0.3g of acetylene black and 0.2g of PEO were weighed and mixed, and stirred in anhydrous acetonitrile for 12 hours. The synthesized slurry is coated on an aluminum foil, dried in a vacuum oven at 80 ℃ for 12h, and processed to manufacture the positive electrode plate LFP. And then, the composite electrolyte membrane LP prepared by the comparative example of the invention is used as an electrolyte to prepare the button cell with the LFP/LP/Li structure, wherein the composite membrane LP is not only the electrolyte but also has the property of a diaphragm. All experiments were performed in a glove box.
2.3 Performance test (1):
the LFP/LPB/Li button cell (LPB-1 from example 1 was the electrolyte) and LFP/LP/Li button cell (LP from comparative example 1 was the electrolyte) fabricated as described above were each placed on a blue tester to test electrical properties. The specific discharge capacity results are shown in fig. 2. Wherein,
the a curve shows the specific discharge capacity of the LFP/LPB/Li battery;
the curve b shows the specific discharge capacity of the LFP/LP/Li battery;
the data summarized by fig. 2 are as follows:
the discharge capacities of the former at 60 ℃ between 2.5 and 3.9V are respectively 158.9, 156, 140.2, 125 and 95mAh/g at 0.1C, 0.2C, 0.5C, 1C and 2C;
the discharge capacities of 0.1C, 0.2C, 0.5C, 1C and 2C of the latter are respectively 85.8 mAh/g, 78.2 mAh/g, 67.5 mAh/g, 48.8 mAh/g and 30.9mAh/g under the condition of 60 ℃ between the voltages of 2.5-3.9V.
In addition, electrochemical impedance spectroscopy analysis is respectively carried out on the LFP/LPB/Li battery and the LFP/LP/Li battery by adopting an electrochemical workstation, the frequency range is 200kHz to 0.1Hz, and the results are as follows:
the conductivity of the former at 60 ℃ is 0.238 mS/cm;
the conductivity of the latter at 60 ℃ was 0.069 mS/cm.
2.4 Performance test (2):
the composite electrolyte membranes LPB-1, LPB-2, LPB-3, LPB-4 and LPB-5 obtained in examples 1 to 5 were electrolytes of LFP/LPB/Li button cells, and were each placed on a blue tester to test electrical properties. The 0.1C specific discharge capacity results are shown in FIG. 3. Wherein,
the a curve shows the specific discharge capacity of the LFP/LPB-1/Li battery;
the curve b shows the specific discharge capacity of the LFP/LPB-2/Li battery;
the c curve shows the specific discharge capacity of the LFP/LPB-3/Li battery;
the d curve shows the specific discharge capacity of the LFP/LPB-4/Li battery;
the e-curve shows the specific discharge capacity of the LFP/LPB-5/Li cell.
The data show that the LPB solid composite electrolyte membrane prepared by the method has superior electrical property compared with the traditional LP composite solid electrolyte membrane, which is mainly because each component in the solid composite electrolyte membrane provided by the invention plays its own role and is effectively synergistic; the inorganic solid electrolyte provides a lithium ion channel, and the composite solid electrolyte has higher mechanical strength; the macromolecular polymer PEO not only can conduct lithium ions, but also can be used as a binder to bond LATP ceramic particles, so that the composite electrolyte membrane is more uniform; the organic electrolyte firstly reduces the crystallinity of PEO and secondly softens the contact between solid and solid interfaces, so that the deposition and the desorption of lithium on the metal lithium can be more uniform, and the electrolyte can well block the generation of lithium dendrites.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A solid composite electrolyte membrane, characterized in that the composite electrolyte membrane is composed of an inorganic solid electrolyte, an organic electrolyte, and a polymer electrolyte.
2. The solid composite electrolyte membrane according to claim 1, wherein the inorganic solid electrolyte is represented by the formula Li1+xAlxTi2–x(PO4)3Wherein 0 < x < 1, preferably x is 0.3.
3. The solid composite electrolyte membrane according to claim 1, wherein the organic electrolyte is an organolithium boron salt;
the polymer electrolyte is polyoxyethylene PEO, polyvinylidene fluoride PVDF, polyacrylonitrile PAN, preferably PEO, and more preferably PEO with a molecular weight of 105～107Still more preferably, it has a molecular weight of 106。
4. A method for producing a solid composite electrolyte membrane, characterized by comprising the steps of:
step 1, preparing an inorganic solid electrolyte through a solid-state reaction;
step 2, preparing an organic electrolyte;
and 3, mixing the product obtained in the step 1, the product obtained in the step 2 and the polymer electrolyte to prepare the solid composite electrolyte membrane.
5. The production method according to claim 4,
in step 1, the inorganic solid electrolyte is made of Li1+xAlxTi2–x(PO4)3Wherein 0 < x < 1, preferably x is 0.3;
in the step 2, the organic electrolyte is organic lithium boron salt;
in step 3, the polymer electrolyte is polyoxyethylene PEO, polyvinylidene fluoride PVDF, polyacrylonitrile PAN, preferably PEO, and more preferably, the molecular weight of PEO is 105～107Still more preferably, it has a molecular weight of 106。
6. The method according to claim 4, wherein the step 1 comprises the following substeps:
substep 1-1: weighing inorganic lithium salt, aluminum oxide, titanium oxide and phosphate according to a stoichiometric ratio, and mixing;
substeps 1-2: calcining the system obtained in the substep 1;
substeps 1-3: and (3) crushing, sintering, crushing again and drying in vacuum to obtain the inorganic solid electrolyte.
7. The production method according to claim 6,
in substep 1-1, the inorganic lithium salt is lithium carbonate or lithium hydroxide, preferably lithium carbonate; the phosphate is ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate, and preferably diammonium hydrogen phosphate;
in the substep 1-2, the calcination temperature is 800-1000 ℃ and the calcination time is 2-3 h;
in the substep 1-3, the crushing is ball milling, the ball milling is carried out by using an organic solvent, the sintering temperature is 800-1000 ℃, and the sintering time is 2-3 h; and the step of re-crushing is ball milling, and the vacuum drying temperature is 80-120 ℃.
8. The method according to claim 4, wherein the step 2 comprises the following substeps:
substep 2-1: dropwise adding the lithium borohydride solution into the tetrahalo-p-xylylene alcohol solution, controlling the dropwise adding temperature to be 40-50 ℃, and after the dropwise adding is finished, carrying out reflux reaction;
substep 2-2: cooling after the reaction is finished, and performing post-treatment to obtain a product;
preferably, the first and second electrodes are formed of a metal,
in the substep 2-1, the tetrahalogen terephthalyl alcohol is tetrafluoroterephthalyl alcohol, tetrachloroterephthalyl alcohol, tetrabromophthalyl alcohol, tetraiodo terephthalyl alcohol, preferably tetrachloroterephthalyl alcohol; the solvent for the solution is tetrahydrofuran, and the reflux reaction time is 6-8 h;
in substep 2-2, the post-treatment comprises filtration and washing of the filter cake with a solvent, followed by vacuum drying of the filter cake at 60-80 ℃ for 24-48 h.
9. The method according to claim 4, wherein in step 3, the preparing step comprises: placing the inorganic solid electrolyte, the organic electrolyte and the polymer electrolyte in a solvent, mixing and stirring uniformly, coating the obtained mixed solution, removing the solvent, and drying in vacuum;
preferably, the first and second electrodes are formed of a metal,
the mass ratio of the inorganic solid electrolyte, the organic electrolyte and the polymer electrolyte is 0.8:0.1:0.1, 0.7:0.15:0.15, preferably 0.7:0.15:0.15,
the solvent is NMP, acetonitrile, preferably acetonitrile,
the temperature for removing the solvent is 60-80 ℃,
the vacuum drying temperature is 70-120 ℃, preferably 80-100 ℃.
10. Use of the solid composite electrolyte membrane according to any one of claims 1 to 3, which is used as an electrolyte of a solid lithium ion battery, wherein the lithium ion battery prepared from the electrolyte has a specific discharge capacity of 158.9mAh/g at 60 ℃ at 0.1C; the specific discharge capacity of 95mAh/g is obtained under the multiplying power of 2C.
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