CN108933281B - Flexible ceramic/polymer composite solid electrolyte and preparation method thereof - Google Patents
Flexible ceramic/polymer composite solid electrolyte and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a flexible ceramic/polymer composite solid electrolyte and a preparation method thereof, wherein monomers of methyl methacrylate, lithium salt, lithium-containing garnet powder and an initiator are mixedAfter standing for a while, the supernatant was aspirated off, and in-situ polymerization was carried out in a closed container at room temperature in an atmosphere to obtain a polymer having a thickness of 50 μm and a lithium ion conductivity of 5 × 10 at room temperature‑4S/cm of composite solid electrolyte. Compared with the prior art, the electrolyte prepared by the invention has the advantages of flexibility, smooth surface, high chemical stability, high lithium ion conductivity, stability to metal lithium and the like.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a flexible ceramic/polymer composite solid electrolyte and a preparation method thereof.
Background
Since birth, the energy density of the lithium ion battery is increased by nearly 2 times, and the lithium ion battery has been widely applied to the production and life of people, so how to further improve the energy density, the capacity density and the safety of the battery is currently the key point of research of the lithium ion battery and is also a hotspot of the energy industry in recent years. The traditional lithium ion battery adopts organic liquid electrolyte, so that the problems of strong side reaction between an electrode and the electrolyte, narrow applicable temperature range, flammable and explosive potential safety hazards and the like can be caused. With respect to these problems, the urgent need for a battery with high safety, high specific capacity and long service life in the future has promoted the development of all-solid-state lithium batteries. The solid electrolyte is used for replacing liquid electrolyte, and the method is an effective way for improving the safety of the lithium ion battery.
The solid electrolyte includes inorganic solid electrolytes and polymer electrolytes, the former of which includes oxide systems and sulfide systems. As a high-performance solid electrolyte, the following requirements should be satisfied: 1. wide electrochemical window and capacity of being charged and dischargedThe lithium ion battery can be suitable for a high-voltage lithium battery material system because the lithium ion battery does not react with positive and negative electrode materials in the process; 2. the lithium ion conductivity is high, and is still generally at least 10 for solid electrolyte systems-4S/cm, the application requirement can be met; 3. the chemical stability is good, the contact with metal lithium is stable, and the stable structure of the surface can be maintained; 4. the mechanical property is good, the processing is suitable, the flexibility is strong, and the interface resistance in contact with the anode and the cathode can be smaller.
In the last decades, lithium-containing garnet LLZO in an oxide system is paid much attention by researchers due to the advantages of strong stability, high room-temperature conductivity, large electrochemical window and the like, and lithium-containing garnet serving as an inorganic oxide ceramic material has high strength and can sufficiently resist the growth of lithium dendrites, and a new way is provided for the use of a metallic lithium negative electrode. However, the lithium-containing garnet has the defects of large interface resistance to metal lithium, unstable cycle, poor flexibility and the like, and the application of the lithium-containing garnet is limited. The polymer electrolyte, which is one of the solid electrolytes, can conduct lithium ions through the movement of the chain segment, and has good viscoelastic deformation capability, but the polymer electrolyte still has the problems of low lithium ion conductivity, poor electrochemical stability, poor mechanical stability and the like, so that the practical application of the polymer electrolyte is limited. Therefore, uniform dispersion of a ceramic phase having high lithium ion conductivity on a polymer matrix is an important direction in the development of solid electrolytes at present. However, how to effectively prepare the ultrathin flexible composite electrolyte with higher ionic conductivity is still one of the problems to be solved urgently in the field.
Disclosure of Invention
The present invention aims to overcome the defects of the prior art and provide a flexible ceramic/polymer composite solid electrolyte with high lithium ion conductivity and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: the solid electrolyte comprises a ceramic phase and a polymer phase doped in the ceramic phase, wherein the ceramic phase is lithium-containing garnet, the polymer phase is polymethyl methacrylate, the crystalline phase of the ceramic phase is a cubic phase garnet structure, the polymer phase forms a flexible network structure in the ceramic phase, and the mass ratio of the ceramic phase to the polymer phase is (50-125): 100. the oxygen-containing group of the polymer has the function of complexing lithium ions, the lithium ions are conducted through the movement of the chain segment, and the polymer can also provide a certain flexible framework.
The grain diameter of the lithium-containing garnet particles in the ceramic phase is 500 nm-5 mu m.
The thickness of the polymer phase is 45-60 mu m.
A method for preparing a flexible ceramic/polymer composite solid electrolyte as described above, comprising the steps of:
(1) mixing monomer methyl methacrylate, lithium salt, lithium-containing garnet powder and an initiator, placing the mixture in water, performing ultrasonic treatment to obtain a suspension, standing the suspension, and removing the supernatant to obtain a lower suspension;
(2) and (2) carrying out in-situ polymerization on the lower-layer suspension obtained in the step (1) in a closed environment to obtain the flexible ceramic/polymer composite solid electrolyte.
In the in-situ polymerization process, the methyl methacrylate is subjected to double bond polymerization under the action of an initiator to form polymethyl methacrylate, and the lithium-containing garnet is not subjected to phase and chemical changes and is uniformly dispersed in a polymer matrix.
The lithium salt comprises one or more of lithium bis (trifluoromethyl) sulfonyl imide, lithium hexafluorophosphate, lithium perchlorate or lithium tetrafluoroborate. The lithium salt is added because the lithium ion conductivity of the polymethyl methacrylate is poor, and the lithium ion conductivity of the polymer phase can be greatly improved after the lithium salt is added.
The particle size of the lithium-containing garnet powder is 500 nm-5 mu m. The lithium-containing garnet powder can be obtained by preparing a lithium-containing garnet solid electrolyte by adopting a solid-phase sintering method and carrying out dry powder ball milling on the solid electrolyte.
The initiator comprises one of azobisisobutyronitrile, azobisisoheptonitrile or dimethyl azobisisobutyrate. The azo initiator is a free radical initiator with nitrogen-nitrogen double bonds, decomposes and initiates all primary reactions, only forms one free radical, has no side reaction, and does not bring other adverse effects on the subsequent formed electrolyte performance.
The mass ratio of the monomer methyl methacrylate, the lithium salt and the lithium-containing garnet powder is (40-50): (5-25): (35-50), wherein the mass ratio of the initiator to the monomer methyl methacrylate is 1: (20-200).
The ultrasonic time is 0-2 h but not 0, and the standing time is 0.5-24 h.
The temperature of the in-situ polymerization is 10-40 ℃, and the time is 6-48 h.
Compared with the prior art, the invention has the beneficial effects that: according to the ultrathin ceramic-polymer composite solid electrolyte prepared by taking methyl methacrylate, lithium salt and lithium-containing garnet powder as raw materials, a small amount of polymethyl methacrylate forms a flexible network in a ceramic phase, lithium ions are mainly conducted through the lithium-containing garnet, the lithium salt-doped polymethyl methacrylate and the lithium-containing garnet have high chemical stability and electrochemical stability and can stably and effectively contact with metal lithium, and therefore the composite electrolyte material has the advantages of high stability, high lithium ion conductivity and stability to the metal lithium.
Drawings
FIG. 1 is an XRD spectrum of the prepared ultrathin ceramic-polymer composite solid electrolyte;
FIG. 2 is a scanning electron microscope image of the surface of the prepared ultrathin ceramic-polymer composite solid electrolyte;
FIG. 3 is a scanning electron microscope image of the cross section of the prepared ultrathin ceramic-polymer composite solid electrolyte
FIG. 4 is an electrochemical impedance spectroscopy analysis chart of the prepared ultrathin ceramic-polymer composite solid electrolyte;
FIG. 5 is a graph showing the thermal weight loss of the prepared ultrathin ceramic-polymer composite solid electrolyte;
FIG. 6 is a cross-sectional line scanning Mapping chart (La element and S element) of the prepared ultra-thin ceramic-polymer composite solid electrolyte.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
In this example, azobisisobutyronitrile was used as the initiator, and lithium bistrifluoromethylsulfonyl imide was used as the lithium salt.
The first step is as follows: mixing monomer methyl methacrylate, lithium-containing garnet powder and lithium bistrifluoromethylsulfonyl imide according to mass fractions of 40%, 20% and 40%, respectively, and adding a solvent according to the mass ratio of methyl methacrylate: adding an initiator into the azodiisobutyronitrile with the mass ratio of 1: 20;
the second step is that: standing the mixture for 12 hours, precipitating, sucking supernatant liquor, and only leaving lower suspension;
the third step: in-situ polymerization was carried out in a closed container environment at a temperature of 10 ℃ and after 6 hours, a flexible and dense conformable electrolyte was obtained.
As can be seen from fig. 1, XRD of the prepared lithium-containing garnet in example 1 is consistent with that of the standard spectrum (JCPDS No.45-0109), and is defined as a cubic phase lithium-containing garnet, which has a certain spread in diffraction peak due to the smaller grain size of the lithium-containing garnet.
Example 2
In this example, azobisisobutyronitrile was used as the initiator, and lithium bistrifluoromethylsulfonyl imide was used as the lithium salt.
The first step is as follows: the monomer methyl methacrylate, lithium-containing garnet powder and lithium bistrifluoromethylsulfonyl imide were mixed in mass fractions of 50%, 5% and 45%, respectively, and the mixture was added as follows: adding an initiator azobisisobutyronitrile into the mixture, wherein the mass ratio of the azobisisobutyronitrile is 1: 50;
the second step is that: standing the mixture for 24 hours, precipitating, sucking supernatant liquor, and only leaving the lower suspension;
the third step: in-situ polymerization was carried out in a closed container environment at a temperature of 15 ℃ and after 24 hours, a flexible and dense conformable electrolyte was obtained.
As can be seen from fig. 2, the surface of the composite electrolyte material prepared in example 2 is uniform and dense, the lithium-containing garnet particles are uniformly distributed on the surface of the electrolyte, the contact performance between the solid electrolyte and the anode and cathode materials is improved, the interface resistance is reduced, and as can be seen by a scanning electron microscope of the cross section, a large amount of lithium-containing garnet ceramic particles exist in the material, the diameter is about 1 to 5 μm, no obvious pores exist, the structure is dense, the lithium ion conductivity of the composite electrolyte can be effectively improved, and the internal resistance of the battery is reduced.
Example 3
In this example, azobisisoheptonitrile was used as the initiator, and lithium hexafluorophosphate was used as the lithium salt.
The first step is as follows: monomer methyl methacrylate, lithium-containing garnet powder and lithium hexafluorophosphate were mixed in mass fractions of 40%, 25% and 35%, respectively, and added as methyl methacrylate: adding an initiator into the azodiisoheptanonitrile with the mass ratio of 1: 200;
the second step is that: standing the mixture for 0.5 hour for precipitation, sucking supernatant liquid, and only leaving the lower suspension;
the third step: and carrying out in-situ polymerization in a closed container environment at the temperature of 40 ℃, and obtaining the flexible and compact composite electrolyte after 48 hours.
As can be seen from fig. 3, the composite electrolyte material prepared in example 3 contains a large amount of lithium-containing garnet ceramic particles, has a diameter of about 1 to 5 μm, has no significant pores, has a compact structure, and can effectively improve the lithium ion conductivity of the composite electrolyte and reduce the internal resistance of the battery.
Example 4
In this example, azobisisoheptonitrile was used as the initiator, and lithium hexafluorophosphate was used as the lithium salt.
The first step is as follows: the monomer methyl methacrylate, lithium-containing garnet powder and lithium hexafluorophosphate were mixed in mass fractions of 45%, 5% and 50%, respectively, and the mixture was added as follows: adding an initiator into the azodiisoheptanonitrile with the mass ratio of 1: 100;
the second step is that: standing the mixture for 16 hours, precipitating, sucking supernatant liquor, and only leaving lower suspension;
the third step: in-situ polymerization was carried out in a closed container environment at a temperature of 30 ℃ and after 12 hours, a flexible and dense conformable electrolyte was obtained.
Electrochemical AC impedance spectroscopy test was performed using the LLZO prepared in this example 4, and it can be seen from FIG. 4 that the high frequency part corresponds to the response of the inside of the composite electrolyte to conductive lithium ions, the lithium ion conductivity of which was 5 × 10-4S/cm of composite solid state.
Example 5
In this example, azobisisoheptonitrile was used as the initiator, and lithium perchlorate was used as the lithium salt.
The first step is as follows: the monomer methyl methacrylate, lithium-containing garnet powder and lithium perchlorate were mixed in mass fractions of 50%, 10% and 40%, respectively, and the mixture was added as follows: adding an initiator into the azodiisoheptanonitrile with the mass ratio of 1: 20;
the second step is that: carrying out ultrasonic treatment on the mixture for 2 hours, standing and precipitating for 12 hours, and then sucking supernatant liquid and only leaving lower-layer suspended matters;
the third step: in-situ polymerization was carried out in a closed container environment at a temperature of 10 ℃ and after 6 hours, a flexible and dense conformable electrolyte was obtained.
The air stability of the composite electrolyte prepared in example 5 is tested, a thermal weight loss curve as shown in fig. 5 is obtained, and it can be roughly observed that the composite electrolyte has three weight loss peaks, the first peak is at 50-100 degrees and corresponds to the moisture absorbed by the material in the air, the second peak is at 250-300 degrees and corresponds to the decomposition process of polymethyl methacrylate, the third peak is about 400-420 degrees earlier, and corresponds to the decomposition process of lithium salt LiTFSi, and the content of the remaining ceramic is about 75%.
Example 6
In this example, azobisisoheptonitrile was used as the initiator, and lithium perchlorate was used as the lithium salt.
The first step is as follows: the monomer methyl methacrylate, lithium-containing garnet powder and lithium perchlorate were mixed in mass fractions of 40%, 5% and 45%, respectively, and the mixture was added as follows: adding an initiator into the azodiisoheptanonitrile with the mass ratio of 1: 50;
the second step is that: carrying out ultrasonic treatment on the mixture for 2 hours, standing and precipitating for 24 hours, and then sucking supernatant liquid and only leaving lower-layer suspended matters;
the third step: in-situ polymerization was carried out in a closed container environment at a temperature of 15 ℃ and after 24 hours, a flexible and dense conformable electrolyte was obtained.
When the cross section of the composite electrolyte prepared in this example 6 is scanned with lines to determine the distribution of the elements La and S, it can be seen that the La and S elements basically show a negative correlation, and the particles in the SEM image all show a high La low S phenomenon, wherein the continuous polymer phase in fig. 6 shows a high S low La phenomenon. This may indicate that the composite electrolyte is a high ionic conductivity lithium-containing garnet particle uniformly distributed in a continuous lithium salt-containing polymer matrix.
Example 7
In this example, dimethyl azodiisobutyrate was used as the initiator, and lithium tetrafluoroborate was used as the lithium salt.
The first step is as follows: monomer methyl methacrylate, lithium-containing garnet powder and lithium tetrafluoroborate were mixed in mass fractions of 40%, 25% and 35%, respectively, and the mixture was added as follows: adding an initiator into dimethyl azodiisobutyrate with the mass ratio of 1: 200;
the second step is that: carrying out ultrasonic treatment on the mixture for 2 hours, standing and precipitating for 0.5 hour, sucking supernatant and only leaving lower-layer suspended matters;
the third step: and carrying out in-situ polymerization in a closed container environment at the temperature of 40 ℃, and obtaining the flexible and compact composite electrolyte after 48 hours.
Example 8
In this example, dimethyl azodiisobutyrate was used as the initiator, and lithium tetrafluoroborate was used as the lithium salt.
The first step is as follows: the monomers methyl methacrylate, lithium-containing garnet powder and lithium tetrafluoroborate were mixed in mass fractions of 45%, 5% and 50%, respectively, and the mixture was added as follows: adding an initiator into dimethyl azodiisobutyrate with the mass ratio of 1: 100;
the second step is that: carrying out ultrasonic treatment on the mixture for 2 hours, standing and precipitating for 16 hours, and sucking supernatant liquid to only leave suspended substances on the lower layer;
the third step: in-situ polymerization was carried out in a closed container environment at a temperature of 30 ℃ and after 12 hours, a flexible and dense conformable electrolyte was obtained.
Claims (10)
1. A preparation method of a flexible ceramic/polymer composite solid electrolyte is characterized by comprising the following steps:
(1) mixing monomer methyl methacrylate, lithium salt, lithium-containing garnet powder and an initiator, placing the mixture in water, performing ultrasonic treatment to obtain a suspension, standing the suspension, and removing the supernatant to obtain a lower suspension;
(2) carrying out in-situ polymerization on the lower-layer suspension obtained in the step (1) in a closed environment to obtain the flexible ceramic/polymer composite solid electrolyte;
the solid electrolyte comprises a ceramic phase and a polymer phase doped in the ceramic phase, wherein the ceramic phase is lithium-containing garnet, the polymer phase is polymethyl methacrylate, the crystalline phase of the ceramic phase is a cubic phase garnet structure, the polymer phase forms a flexible network structure in the ceramic phase, and the mass ratio of the ceramic phase to the polymer phase is (50-125): 100.
2. the method of claim 1, wherein the lithium salt comprises one or more of lithium bis (trifluoromethylsulfonyl) imide, lithium hexafluorophosphate, lithium perchlorate, or lithium tetrafluoroborate.
3. The method of claim 1, wherein the lithium-containing garnet powder has a particle size of 500nm to 5 μm.
4. The method of claim 1, wherein the initiator comprises one of azobisisobutyronitrile, azobisisoheptonitrile, or dimethyl azobisisobutyrate.
5. The method for preparing the flexible ceramic/polymer composite solid electrolyte according to claim 1, wherein the mass ratio of the monomers of methyl methacrylate, lithium salt and lithium-containing garnet powder is (40-50): (5-25): (35-50), wherein the mass ratio of the initiator to the monomer methyl methacrylate is 1: (20-200).
6. The method for preparing the flexible ceramic/polymer composite solid electrolyte according to claim 1, wherein the ultrasonic time is 0-2 h and is not 0, and the standing time is 0.5-24 h.
7. The method for preparing the flexible ceramic/polymer composite solid electrolyte according to claim 1, wherein the temperature of the in-situ polymerization is 10-40 ℃ and the time is 6-48 h.
8. A flexible ceramic/polymer composite solid electrolyte obtained by the production method according to claim 1.
9. The flexible ceramic/polymer composite solid electrolyte of claim 8, wherein the lithium-containing garnet particles in the ceramic phase have a particle size of 500nm to 5 μm.
10. The flexible ceramic/polymer composite solid electrolyte of claim 8, wherein the polymer phase has a thickness of 45 to 60 μm.
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