CN109755637B - Oxide ceramic composite solid electrolyte, preparation method and application thereof - Google Patents
Oxide ceramic composite solid electrolyte, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an oxide ceramic composite solid electrolyte, a preparation method and application thereof. The oxide ceramic composite solid electrolyte comprises the following components: 20 wt.% to 50 wt.% tantalum-doped garnet-type oxide ceramic; 30 wt.% to 60 wt.% of a polymer electrolyte; 10 wt.% to 30 wt.% lithium salt; and 5 wt.% to 20 wt.% of fluorine-containing imidazole ionic liquid. The preparation method of the oxide ceramic composite solid electrolyte comprises a preparation step, a sintering step and a mixing step. The preparation method comprises the following steps: weighing lithium source and La2O3、ZrO2And Ta2O5Adding the mixture and isopropanol into a ball milling tank for ball milling; sintering: removing isopropanol from the material obtained after ball milling, performing presintering, and performing secondary sintering after re-grinding to obtain oxide ceramic; and a mixing step: adding the tantalum-doped garnet-type oxide ceramic, polymer electrolyte, lithium salt and ionic liquid into an organic solvent, uniformly dispersing, pouring into a mold, and volatilizing the organic solvent to obtain the oxide ceramic composite electrolyte.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to an oxide ceramic composite solid electrolyte, a preparation method and application thereof.
Background
The lithium ion battery has become the most widely used rechargeable battery by virtue of the advantages of high specific energy, long cycle life, high rated voltage, low self-discharge rate, environmental protection and the like. However, the current lithium ion battery generally adopts organic electrolyte, has the problems of easy decomposition at high temperature, flammability, narrow electrochemical window and the like, and is a key factor for restricting the safety and energy density of the battery. Compared with the traditional electrolyte, the solid electrolyte does not contain flammable and volatile components, has good compatibility with metallic lithium, wide electrochemical stability window and large energy density promotion space. In addition, the solid-state lithium battery also has the advantages of low self-discharge rate, good high-temperature adaptability and the like.
The ionic conductivity of the oxide solid electrolyte is between that of sulfide and polymer, the preparation process has low requirement on environment, and compared with sulfide electrolyte, the oxide solid electrolyte is easier to realize large-scale production. Wherein, the ion conductivity of the garnet-structured lithium lanthanum zirconium oxide electrolyte at room temperature can reach up to 10-3S/cm, stability to metal lithium, wide electrochemical window and great application potential. However, like other inorganic solid electrolytes, the ceramic sheet prepared from the pure lithium lanthanum zirconium oxide ceramic has poor contact with the positive and negative electrode interfaces, high interfacial resistance, poor mechanical properties, and easy cracking under pressure, and is not favorable for large-scale battery assembly and improvement of battery performance.
In order to solve the problem of contact between the inorganic electrolyte and the interfaces of the positive electrode and the negative electrode, a commonly adopted strategy is to compound the inorganic electrolyte and the polymer electrolyte and improve the contact degree between the inorganic electrolyte and the positive electrode and the negative electrode by utilizing the flexibility and viscoelasticity of the polymer. In the prior art, a composite solid electrolyte of a lithium ion battery and a preparation method thereof are adopted, a composite membrane of an inorganic fast ion conductor and a polymer is prepared by electrostatic spinning and dipping, but the volume change generated in the process of lithium desorption of an electrode material is difficult to compensate only by the elasticity of the polymer, the interface problem still exists, and the problem is worsened along with the progress of charge and discharge cycles. There are also prior art techniques that improve the electrode/electrolyte interface contact problem in solid state batteries using small amounts of liquid electrolyte, but the presence of electrolyte still presents a safety problem.
Disclosure of Invention
The invention aims to provide an oxide ceramic composite solid electrolyte, a preparation method and application thereof, and aims to provide the electrolyte which has high conductivity, good mechanical strength and viscoelasticity, good contact with an electrode interface and electrical property and safety performance.
In order to solve the technical problems, the invention provides an oxide ceramic composite solid electrolyte, which comprises the following components: 20 wt.% to 50 wt.% tantalum-doped garnet-type oxide ceramic; 30 wt.% to 60 wt.% of a polymer electrolyte; 10 wt.% to 30 wt.% lithium salt; and 5 wt.% to 20 wt.% ionic liquid. Wherein, the conduction of lithium ions is not facilitated when the content of lithium salt is too low, the preparation cost is increased when the content of lithium salt is too high, and the mechanical property of the composite membrane is reduced. Too low content of ionic liquid can not achieve the effect of enhancing interface contact, and too high content can reduce the strength of the electrolyte membrane, improve the preparation cost and have the possibility of liquid leakage.
Optionally, the tantalum-doped garnet-type oxide ceramic is lithium lanthanum zirconium oxide doped with tantalum or codoped with tantalum and other elements; the polymer electrolyte comprises polypropylene carbonate and polyethylene oxide; the lithium salt comprises one or more of lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide, lithium tris (trifluoromethanesulfonate) methide and lithium tetrafluoroborate.
Optionally, the ionic liquid is fluorine-containing imidazole ionic liquid; the fluorine-containing ionic liquid can react with lithium to generate a fluorine-containing compound while plasticizing and improving interface contact, thereby inhibiting the growth of lithium dendrites and improving the chemical stability of an electrolyte and a lithium negative electrode.
Optionally, the mass percentage of the polypropylene carbonate in the polymer electrolyte is 10 wt.% to 50 wt.%. Within the composition range, the polymer film is comprehensively balanced in the aspects of ionic conductivity, film forming capability, mechanical strength, viscoelasticity and the like.
Optionally, the other elements include one or more of barium, aluminum, niobium, antimony, magnesium, calcium, tin, rubidium, and gallium.
Optionally, the fluorine-containing imidazole ionic liquid is selected from one or more of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-propyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole tetrafluoroborate.
Optionally, the particle size of the tantalum-doped garnet-type oxide ceramic is 400nm to 700 nm. Within this size range, the ceramic particles can be uniformly distributed in the polymer. The particle size is too large, and the tantalum-doped garnet-type oxide ceramic particles are not easy to uniformly disperse in the polymer; if the particle size is too small, the ceramic particles are easily agglomerated.
The invention also provides a preparation method of the oxide ceramic composite solid electrolyte, which comprises a preparation step, a sintering step and a mixing step. The preparation method comprises the following steps: weighing lithium source and La2O3、ZrO2And Ta2O5Adding the mixture and isopropanol into a ball milling tank for ball milling; sintering: removing isopropanol from the material obtained after ball milling, performing presintering, and performing secondary sintering after re-grinding to obtain tantalum-doped garnet oxide ceramic; and a mixing step: adding the tantalum-doped garnet-type oxide ceramic, a polymer electrolyte, a lithium salt and an ionic liquid into an organic solvent, uniformly dispersing, pouring into a mold, and volatilizing the organic solvent to obtain the tantalum-doped garnet-type oxide ceramic composite electrolyte; wherein, the lithium source, La2O3、ZrO2And Ta2O5The molar ratio of (1) to (1.0) to (7.0) to (2.9) to (3.0). In order to compensate the loss of lithium during sintering, the lithium source is excessive by 10-20%.
According to the aspect of the invention, the preparation steps further comprise weighing other element raw materials, adding the other element raw materials and the organic solvent into a ball milling tank for ball milling, wherein the ball milling rotation speed is 150-300 rpm, and the ball milling time is 8-24 h; lithium source, La2O3、ZrO2、Ta2O5And the molar ratio of the other element raw materials is (6.0-7.0): (2.9-3.0): (1.0-1.9): (0.1-1.0): (0-0.5), and under the molar ratio, the prepared tantalum doped garnet type oxide ceramic is in a cubic phase and has high ionic conductivity.
According to the aspect of the invention, the pre-sintering temperature is 800-1000 ℃, and the pre-sintering time is 6-16 h; the temperature of the secondary sintering is 1100-1200 ℃, and the time of the secondary sintering is 16-30 h. The technological parameters of pre-sintering and secondary sintering are closely related, and the parameters are limited to produce the cubic phase tantalum-doped garnet oxide ceramic composite solid electrolyte with small particle size and uniform size distribution.
The organic solvent is one or more of N-methyl pyrrolidone, anhydrous acetonitrile, dimethyl sulfoxide and N, N-dimethylformamide, and the dispersion in the mixing step is carried out under stirring at the temperature of 20-60 ℃ for 24-48 h; the organic solvent is volatilized at the temperature of 20-50 ℃, the solvent is dried by distillation and then is dried in vacuum at the temperature of 40-60 ℃ for 12-24 h, the temperature and the time of the stirring, the volatilization and the vacuum drying are mutually related, and experiments prove that the composite solid electrolyte with good film forming capability, excellent mechanical strength, less bubbles and uniform ceramic particle dispersion can be prepared by the limitation of the parameters.
The invention also provides an application of the composite solid electrolyte, such as the oxide ceramic, and the tantalum-doped garnet-type oxide ceramic composite solid electrolyte is used in lithium ion batteries, lithium sulfur batteries and lithium air batteries.
In conclusion, the oxide ceramic composite solid electrolyte provided by the invention is composed of the tantalum-doped garnet-type oxide ceramic, a polymer electrolyte, a lithium salt and an ionic liquid. The invention utilizes tantalum-doped lithium lanthanum zirconium oxide to improve the ionic conductivity of the composite membrane and simultaneously improve the chemical compatibility of the electrolyte and the electrode, particularly the lithium cathode; the polypropylene carbonate is utilized to improve the amorphous degree, the ionic conductivity and the viscoelasticity of the polymer; the mechanical strength and the chemical stability of the electrolyte membrane are improved by using the polyethylene oxide; the fluorine-containing imidazole ionic liquid is used for plasticizing, so that the contact between an electrolyte and an electrode interface can be improved, the generation of lithium dendrites can be inhibited, meanwhile, the ionic liquid is nonflammable, oxidation-resistant, good in thermal stability and lithium salt solubility, and the safety performance of the solid-state battery is ensured.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a tantalum-doped garnet-type oxide ceramic provided in accordance with one embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of a tantalum-doped garnet-type oxide ceramic provided in accordance with an embodiment of the present invention;
fig. 3 is a digital photograph of an oxide ceramic composite solid electrolyte provided in accordance with an embodiment of the present invention;
FIG. 4 is a scanning electron microscope image of an oxide ceramic composite solid electrolyte provided in the first embodiment of the present invention;
FIG. 5 is an AC impedance curve of an oxide ceramic composite solid electrolyte provided in accordance with one embodiment of the present invention;
fig. 6 is a constant current charge-discharge cycle test curve of a lithium ion battery assembled with an oxide ceramic composite solid electrolyte provided in a first embodiment of the present invention;
fig. 7 is a graph of capacitance cycle performance of a lithium ion battery assembled with an oxide ceramic composite solid electrolyte according to a first embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The chemical formula of lithium bis (trifluoromethanesulfonate) imide in the present invention is LiN (SO)2CF3)2In the present invention, tris (trifluoromethanesulfonic) methyllithium is represented by the formula LiC (SO)2CF3)3。
Example one
Preparation of garnet ceramic electrolyte Li by traditional solid-phase sintering method6.4La3Zr1.4Ta0.6O12. Weighing Li according to stoichiometric ratio2CO3、La2O3、ZrO2And Ta2O5And adding the mixture and 30ml of isopropanol into a ball milling tank, and carrying out ball milling for 20 hours at the rotating speed of 250 rpm. To compensate for the loss of lithium volatilization during high temperature calcination, Li is set2CO3Excess of 10%. And drying the mixed solution in a forced air oven at 80 ℃ for 12h after the ball milling is finished to obtain precursor powder. Transferring the obtained powder to a porcelain boat in a tube furnaceCalcining at 900 ℃ for 8h in the atmosphere of medium air. The pre-sintered powder is ground again and then calcined in air at 1100 ℃ for 24h to obtain cubic phase Li6.4La3Zr1.4Ta0.6O12。
0.8 g of polyethylene oxide and 0.8 g of polypropylene carbonate were weighed into 50ml of anhydrous acetonitrile and sufficiently stirred at 50 ℃. After the polymer solution was dispersed uniformly, 0.32 g of lithium bis (trifluoromethanesulfonate) imide and 0.48 g of Li were added6.4La3Zr1.4Ta0.6O12And 0.13 g of 1-butyl-3-methylimidazolium tetrafluoroborate, stirred at 50 ℃ for 48 h. And pouring the obtained uniform viscous colloid into a polytetrafluoroethylene forming die, opening and drying in a glove box, transferring the die into a vacuum oven at 50 ℃ after the solvent is evaporated, and drying in vacuum for 24 hours to obtain the oxide ceramic composite electrolyte membrane by stripping.
XRD test of the tantalum-doped garnet-type oxide ceramic powder prepared in the first example showed that the XRD spectrum of the product was consistent with the diffraction spectrum of cubic-phase lithium lanthanum zirconium oxide as shown in FIG. 1. Scanning Electron Microscope (SEM) tests were performed on the tantalum-doped garnet-type oxide ceramic powder prepared in the first embodiment, and it can be seen from fig. 2 that the ceramic particles have a uniform size of about 200nm to 400 nm. FIG. 3 is a digital photograph of an oxide ceramic composite electrolyte membrane prepared in the first embodiment, and it can be seen that the formulation is capable of forming a membrane well, and the oxide ceramic is uniformly distributed in the polymer, and the thickness of the composite membrane measured by a thickness gauge is about 100 μm. Fig. 4 is an SEM image of the oxide ceramic composite solid electrolyte prepared in the first embodiment of the present invention, and it can be seen that the surface of the composite membrane is relatively flat, and the oxide ceramic particles are relatively uniformly distributed in the polymer matrix.
The oxide ceramic composite membrane prepared in the first embodiment is assembled into a symmetrical blocking button cell, a stainless steel gasket is used as a blocking electrode, an alternating current impedance test is carried out on the cell, the frequency range is 2M Hz-1 Hz, the amplitude is 10mV, the obtained alternating current impedance spectrum is shown in figure 5, and the room temperature ionic conductivity of the composite membrane is calculated to be 1.58nm multiplied by 10-4S/cm。
The oxide ceramic composite membrane prepared in the first embodiment is used as an electrolyte, and the anode is composed ofLithium iron phosphate, Li6.4La3Zr1.4Ta0.6O12The superconducting carbon black (Super P) and polyvinylidene fluoride (PVDF) are formed according to the mass ratio of 75: 9: 10: 6, and the negative electrode is metallic lithium. The assembled button cell is subjected to a room temperature 0.1C constant current charge-discharge cycle test, the obtained charge-discharge curve and cycle performance are shown in figure 6, the initial specific capacity is 156.6mAh/g, and the capacity retention rate is 94.6% after 30-week cycle.
Example two
Preparation of garnet ceramic electrolyte Li by traditional solid-phase sintering method6.2Al0.2La3Zr1.8Ta0.2O12. Weighing LiOH and Al according to stoichiometric ratio2O3、La2O3、ZrO2And Ta2O5And adding the mixture and 50ml of isopropanol into a ball milling tank, and carrying out ball milling for 24 hours at the rotating speed of 300 rpm. To compensate for the loss of lithium volatilization during high temperature calcination, a 15% excess of LiOH was set. And drying the mixed solution in a forced air oven at 60 ℃ for 8h after the ball milling is finished to obtain precursor powder. The powder obtained was transferred to a porcelain boat and calcined in a tube furnace at 800 ℃ for 6h in air atmosphere. The pre-sintered powder is ground again and then calcined in the air at 1050 ℃ for 20h to obtain cubic phase Li6.2Al0.2La3Zr1.8Ta0.2O12。
1.4 g of polyethylene oxide and 0.2 g of polypropylene carbonate were weighed into 50ml of N-methylpyrrolidone and stirred well at 30 ℃. After the polymer solution was dispersed uniformly, 0.48 g of lithium hexafluorophosphate, 0.64 g of tantalum-doped garnet-type oxide ceramic and 0.24 g of 1-propyl-3-methylimidazolium tetrafluoroborate were added and stirred at 30 ℃ for 24 hours. And pouring the obtained uniform viscous colloid into a polytetrafluoroethylene forming die, drying the die with an opening at 40 ℃, transferring the die into a vacuum oven at 40 ℃ after the solvent is evaporated, and drying the die in vacuum for 20 hours to obtain the oxide ceramic composite electrolyte membrane by stripping.
XRD and SEM tests of the tantalum-doped garnet oxide ceramic powder prepared in the embodiment show that the XRD spectrum of the product is consistent with the diffraction spectrum of cubic phase lithium lanthanum zirconium oxygen, and the particle size of the tantalum-doped garnet oxide ceramic is uniform and is about 200-300 nm. The oxide ceramic composite electrolyte prepared by the embodiment has good film forming capability, no obvious bubbles and uniform ceramic particle distribution, and the thickness of the composite film measured by a thickness meter is about 150 mu m. SEM pictures of the composite film show that the surface of the composite film is flat and uniform, and tantalum-doped garnet-type oxide ceramic particles are uniformly distributed in a polymer matrix.
The oxide ceramic composite membrane prepared in the embodiment is assembled into a symmetrical blocking button cell, a stainless steel gasket is used as a blocking electrode, an alternating current impedance test is carried out on the cell, the frequency range is 2M Hz-1 Hz, the amplitude is 10mV, and the room temperature ionic conductivity of the composite membrane is calculated to be 1.32 multiplied by 10 according to the obtained alternating current impedance spectrum-4S/cm。
The oxide ceramic composite membrane prepared by the embodiment is used as an electrolyte, and the anode is made of lithium iron phosphate and Li6.2Al0.2La3Zr1.8Ta0.2O12The Super P and PVDF are mixed according to the mass ratio of 75: 9: 10: 6, and the negative electrode is metallic lithium. The assembled button battery is subjected to 0.1C constant-current charge-discharge circulation, the initial specific capacity is 150.3mAh/g, and the capacity retention rate is 93.3% after 30-week circulation.
EXAMPLE III
Preparation of garnet ceramic electrolyte Li by traditional solid-phase sintering method6.35La2.95Rb0.05Zr1.2Ta0.8O12. Weighing LiOH. H according to stoichiometric ratio2O、La2O3、Rb2CO3、ZrO2And Ta2O5And adding the mixture and 50ml of isopropanol into a ball milling tank, and carrying out ball milling for 16h at the rotating speed of 200 rpm. To compensate for the loss of lithium volatilization during high temperature calcination, a 10% excess of lithium source was set. And drying the mixed solution in a forced air oven at 60 ℃ for 24h after the ball milling is finished to obtain precursor powder. The powder obtained was transferred to a porcelain boat and calcined in a tube furnace at 900 ℃ for 12h in air atmosphere. The pre-sintered powder is ground again and then calcined in air at 1200 ℃ for 24h to obtain cubic phase Li6.35La2.95Rb0.05Zr1.2Ta0.8O12。
1.12 g of poly are weighedEthylene oxide and 0.48 g of polypropylene carbonate were added to 50ml of N, N-dimethylformamide and stirred well at 40 ℃. After the polymer solution was dispersed uniformly, 0.16 g of lithium perchlorate and 0.32 g of Li were added6.35La2.95Rb0.05Zr1.2Ta0.8O12And 0.16 g of 1-ethyl-3-methylimidazolium tetrafluoroborate, stirred at 55 ℃ for 24 h. And pouring the obtained uniform viscous colloid into a polytetrafluoroethylene forming die, drying the colloid in an open manner at 50 ℃, transferring the die into a vacuum oven at 50 ℃ after the solvent is evaporated, and drying the die in vacuum for 18 hours to obtain the oxide ceramic composite electrolyte membrane by stripping.
XRD and SEM tests of the tantalum-doped garnet oxide ceramic powder prepared in the embodiment show that the XRD spectrum of the product is consistent with the diffraction spectrum of cubic phase lithium lanthanum zirconium oxygen, and the particle size of the tantalum-doped garnet oxide ceramic is uniform and is about 500-700 nm. The oxide ceramic composite electrolyte prepared by the embodiment has good film forming capability, no obvious bubbles and uniform ceramic particle distribution, and the thickness of the composite film measured by a thickness meter is about 120 mu m. SEM pictures of the composite film show that the surface of the composite film is flat and uniform, and tantalum-doped garnet-type oxide ceramic particles are uniformly distributed in a polymer matrix.
The oxide ceramic composite membrane prepared in the embodiment is assembled into a symmetrical blocking button cell, a stainless steel gasket is used as a blocking electrode, an alternating current impedance test is carried out on the cell, the frequency range is 2M Hz-1 Hz, the amplitude is 10mV, and the room temperature ionic conductivity of the composite membrane is calculated to be 1.02 multiplied by 10 according to the obtained alternating current impedance spectrum-4S/cm。
The oxide ceramic composite membrane prepared by the embodiment is used as an electrolyte, and the anode is made of lithium iron phosphate and Li6.35La2.95Rb0.05Zr1.2Ta0.8O12The Super P and PVDF are mixed according to the mass ratio of 75: 9: 10: 6, and the negative electrode is metallic lithium. The assembled button battery is subjected to 0.1C constant-current charge-discharge circulation, the initial specific capacity is 148.8mAh/g, and the capacity retention rate is 95.3% after 30-week circulation.
Comparative example 1
The preparation method of oxide ceramic composite solid electrolyte is basicallyThe same as in example one, except that 0.8 g of polyvinylidene fluoride-hexafluoropropylene was substituted for 0.8 g of polyethylene oxide in the polymer. The obtained composite film has good mechanical strength, but low lithium ion conductivity at room temperature, 5.48 × 10-6S/cm. The button cell is assembled according to the same parameters, and a 0.1C constant-current charge-discharge cycle test is carried out at room temperature, so that the initial specific capacity is 155.9mAh/g, and the discharge capacity is rapidly reduced to 13mAh/g from the 3 rd week.
The first comparative example and the first comparative example show that the electrochemical performance of the lithium ion battery prepared by using the polyethylene oxide is more excellent than that of vinylidene fluoride-hexafluoropropylene due to the high room temperature lithium ion conductivity.
The oxide ceramic composite solid electrolyte provided by the invention is composed of tantalum-doped garnet-type oxide ceramic, polymer electrolyte, lithium salt and ionic liquid. The invention utilizes tantalum-doped lithium lanthanum zirconium oxide to improve the ionic conductivity of the composite membrane and simultaneously improve the chemical compatibility of the electrolyte and the electrode, particularly the lithium cathode; the polypropylene carbonate is utilized to improve the amorphous degree, the ionic conductivity and the viscoelasticity of the polymer; the mechanical strength and the chemical stability of the electrolyte membrane are improved by using the polyethylene oxide; the fluorine-containing imidazole ionic liquid is used for plasticizing, so that the contact between an electrolyte and an electrode interface can be improved, the growth of lithium dendrites can be inhibited, meanwhile, the ionic liquid is nonflammable, oxidation-resistant, good in thermal stability and lithium salt solubility, and the safety performance of the solid-state battery is ensured.
Moreover, the tantalum-doped garnet-type oxide ceramic provided by the invention is doped with cubic-phase lithium lanthanum zirconium tantalum oxygen, has stable particle size and uniform distribution, can construct an ion conduction channel when doped into a polymer, and simultaneously improves the amorphous degree of the polymer and widens the electrochemical window; the polymer is polyoxyethylene and polypropylene carbonate, the polyoxyethylene has good chemical stability and mechanical strength, the polypropylene carbonate is high in amorphous degree, the ionic conductivity of the composite membrane can be improved, meanwhile, the viscoelasticity of the composite membrane is increased, and the contact degree of the composite membrane and an electrode material is improved.
Secondly, the oxide ceramic composite solid electrolyte is added with fluorine-containing ionic liquid, so that on one hand, the volume change of the electrode in the lithium desorption process is compensated, and the interface contact between the electrode and the electrolyte is improved; on the other hand, the fluorine-containing ionic liquid can generate chemical reaction with the negative electrode lithium metal, so that a fluorine-containing compound is generated on the surface of lithium, the growth of lithium dendrite is inhibited, and the interface stability of the electrolyte and the negative electrode lithium is improved.
In addition, the oxide ceramic electrolyte is prepared by a solid phase method, the process is simple, and the large-scale production is easy to realize. Tantalum doping or tantalum and metal element co-doping is selected, so that the cubic structure of the lithium lanthanum zirconium oxide electrolyte can be stabilized, and higher ionic conductivity can be obtained.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. An oxide ceramic composite solid electrolyte is characterized by comprising the following components:
20 wt.% to 50 wt.% tantalum and rubidium co-doped cubic phase garnet type oxide ceramic;
30 wt.% to 60 wt.% of a polymer electrolyte;
10 wt.% to 30 wt.% lithium salt; and
5 wt% -20 wt% of fluorine-containing imidazole ionic liquid;
wherein the polymer electrolyte comprises polypropylene carbonate and polyethylene oxide;
wherein the fluorine-containing imidazole ionic liquid is selected from one or more of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-propyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole tetrafluoroborate.
2. The oxide ceramic composite solid electrolyte of claim 1, wherein the lithium salt comprises one or more of lithium bis (trifluoromethylsulfonate) imide, lithium hexafluorophosphate.
3. The oxide-ceramic composite solid electrolyte of claim 1, wherein the tantalum and rubidium co-doped garnet-type oxide ceramic is li6.35la2.95rb0.05zr1.2ta0.8o12.
4. The oxide ceramic composite solid electrolyte of claim 1, wherein the polymer electrolyte comprises 10 wt.% to 50 wt.% of polypropylene carbonate.
5. The oxide ceramic composite solid electrolyte according to claim 1, wherein the particle size of the tantalum and rubidium co-doped garnet-type oxide ceramic is 400nm to 700 nm.
6. A production method of the oxide ceramic composite solid electrolyte according to any one of claims 1 to 5, characterized by comprising:
the preparation method comprises the following steps: weighing a lithium source, La2O3, Rb2CO3, ZrO2 and Ta2O5, and adding the materials and isopropanol into a ball milling tank for ball milling;
sintering: removing isopropanol from the material obtained after ball milling, performing presintering, grinding again, and performing secondary sintering to obtain tantalum and rubidium co-doped garnet type oxide ceramic; and
mixing: adding tantalum and rubidium co-doped garnet type oxide ceramic, polymer electrolyte, lithium salt and fluorine-containing imidazole ionic liquid into an organic solvent, uniformly dispersing, pouring into a mold, and volatilizing the organic solvent to obtain the tantalum-doped garnet type oxide ceramic composite electrolyte;
wherein the molar ratio of the lithium source to the La2O3 to the ZrO2 to the Ta2O5 is 6.0-7.0: 2.9-3.0: 1.0-1.9: 0.1-1.0.
7. The preparation method of the oxide ceramic composite solid electrolyte according to claim 6, wherein the preparation step further comprises weighing other element raw materials and adding the other element raw materials and the organic solvent into a ball milling tank for ball milling, wherein the rotation speed of the ball milling is 150-300 rpm, and the ball milling time is 8-24 h; the molar ratio of the lithium source, La2O3, ZrO2, Ta2O5 and other element raw materials is 6.0-7.0: 2.9-3.0: 1.0-1.9: 0.1-1.0: 0-0.5.
8. The method for preparing the oxide ceramic composite solid electrolyte according to claim 6, wherein the pre-sintering temperature is 800 ℃ to 1000 ℃, and the pre-sintering time is 6h to 16 h; the temperature of the secondary sintering is 1100-1200 ℃, and the time of the secondary sintering is 16-30 h; the organic solvent is one or more of N-methyl pyrrolidone, anhydrous acetonitrile, dimethyl sulfoxide and N, N-dimethylformamide, and the dispersion in the mixing step is carried out under stirring at the temperature of 20-60 ℃ for 24-48 h; the organic solvent volatilization is carried out at 20-50 ℃, and the solvent is dried by distillation and then is dried in vacuum at 40-60 ℃ for 12-24 hours.
9. Use of the oxide ceramic composite solid electrolyte according to any one of claims 1 to 5, wherein the oxide ceramic composite solid electrolyte is used in lithium ion batteries, lithium sulfur batteries and lithium air batteries.
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| US20220344707A1 (en) * | 2019-09-26 | 2022-10-27 | Fuji Pigment Co., Ltd. | Composite oxide powder, method for producing composite oxide powder, method for producing solid electrolyte object, and method for producing lithium ion secondary battery |
| JP6695560B1 (en) * | 2019-09-26 | 2020-05-20 | 冨士色素株式会社 | Composite oxide powder, method for producing composite oxide powder, method for producing solid electrolyte body, and method for producing lithium ion secondary battery |
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