CN109818051A - Lithium lanthanum zirconium oxygen solid electrolyte and preparation method thereof, lithium ion battery - Google Patents
Lithium lanthanum zirconium oxygen solid electrolyte and preparation method thereof, lithium ion battery Download PDFInfo
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Abstract
The invention belongs to solid lithium battery fields, disclose a kind of lithium lanthanum zirconium oxygen solid electrolyte, the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen is compound in including 60~75wt% polymer, 8~15wt% lithium salts and the three-dimensional porous inorganic network of 15~30wt% lithium lanthanum zirconium oxygen, the polymer in situ.The invention also discloses the preparation method of lithium lanthanum zirconium oxygen solid electrolyte and its field of lithium ion battery application.Lithium lanthanum zirconium oxygen three-dimensional porous network provides continuous lithium ion transport channel, keeps ionic conductivity higher.Meanwhile the composite solid electrolyte that exists for of lithium lanthanum zirconium oxygen three-dimensional porous network provides certain mechanical property, is able to suppress the growth of Li dendrite, improves the high-temperature behavior and safety of battery.To optimization and solid electrolyte and interelectrode interface compatibility and stability are improved, the solid lithium battery thus formed has the advantages that stable cycle performance, high rate performance are high, interface impedance is low, stability is good.
Description
Technical field
The invention belongs to solid lithium battery field more particularly to composite solid electrolyte, specifically a kind of lithium lanthanum zirconium oxygen
Solid electrolyte and preparation method thereof and its field of lithium ion battery application.
Background technique
Lithium metal battery has been widely regarded as most promising next-generation energy storage device due to its high energy density.
However, facing the leakage of electrolyte using the lithium metal battery of organic liquid electrolyte and burning and being caused by lithium dendrite growth
The security risks such as short circuit.Traditional organic liquid electrolyte is substituted using solid electrolyte and is assembled into solid lithium battery, is had
Hope the safety for fundamentally improving lithium battery.Common solid electrolyte is divided into polymerization solid electrolyte and inorganic solid-state electrolysis
Matter.However some shortcomings are usually present using single electrolyte.Solid polyelectrolyte has between good flexible and electrode
Interfacial contact it is more preferable, but low ionic conductivity, narrow electrochemical window limit the development of solid polyelectrolyte
With application.Inorganic solid electrolyte has the advantages of high ionic conductivity, wide electrochemical window, but its with it is interelectrode
Interfacial contact is poor, constrains the application of inorganic solid electrolyte to the problems such as water and sensitive oxygen.Composite solid electrolyte is comprehensive poly-
Close object solid electrolyte and the advantages of inorganic solid electrolyte, ionic conductivity be high, and electrochemical stability is good, good mechanical property with
And it is easy to form.
Polyethylene glycol oxide is widely studied because of it with good interface compatibility and good lithium salts solvability.It is inorganic
Due to conductivity at room temperature height, the advantages that electrochemical stability is good, is widely used in compound lithium lanthanum zirconium oxygen in solid electrolyte
In solid state electrolysis Quality Research.For example, obtaining composite solid by the way that lithium lanthanum zirconium oxygen particle to be distributed in polyethylene glycol oxide matrix
Dielectric film (J.Zhang et al.Nano Energy, 2016,28,447-454), utilizes the boundary of particle and polymeric matrix
Face effect improves composite solid electrolyte film properties, but lithium lanthanum zirconium oxygen particle exists with discrete form, does not form continuous lithium
Ion transmission channel, ionic conductivity are low.On this basis, there is work in order to expand lithium ion mobility channel, pass through Static Spinning
Silk obtains the lithium lanthanum Zirconia fibers film with tridimensional network, and with polyethylene glycol oxide and lithium salts are compound obtains flexible compound electricity
Not only room-temperature ion is electric for the composite solid electrolyte that solution matter (K, Fu et al.PNAS, 2016,113 (26), 7094) is prepared
Conductance is high, and stablizes to lithium.But electrostatic spinning is at high cost, is not suitable for large-scale application, it is, thus, sought for efficient cost
Cheap technology prepares lithium lanthanum zirconium oxygen nanofiber.Using a kind of new strategy, lithium lanthanum zirconium oxygen net is prepared by template of cellulose
Network, then high, telescopic composite solid electrolyte (H, Xie with the compound conductivity at room temperature that obtains of polyethylene glycol oxide and lithium salts
et al.Adv.Energy Mater.,2018,8,1703474.)
As can be seen that there are still chemical properties and mechanical property to get both for existing composite solid electrolyte, cost
The problems such as high preparation method is complicated, therefore, it is necessary to develop a kind of new composite solid electrolyte and preparation method thereof.
Summary of the invention
For the problem present on, the object of the present invention is to provide a kind of lithium lanthanum zirconium oxygen three-dimensional porous networks and its compound
The preparation method of solid electrolyte；Three-dimensional porous lithium lanthanum zirconium oxygen network with continuous lithium ion transport channel is solid for flexible compound
State electrolyte provides higher ionic conductivity and certain mechanical strength.
In order to achieve the above objectives, the invention adopts the following technical scheme:
The present invention is compound using the lithium three-dimensional porous inorganic network of lanthanum zirconium oxygen and polymer, lithium salts of template preparation, obtains
Flexible compound solid electrolyte；It includes 60~75wt% polymer, 8~15wt% lithium salts and 15~30wt% lithium lanthanum zirconium oxygen three
Porous, inorganic network is tieed up, the polymer in situ is compound in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen.
Further, the polymer is selected from polyethylene glycol oxide, polyacrylonitrile, Kynoar, poly-methyl methacrylate
At least one of ester, polypropylene oxide, polyvinylpyrrolidone, Vingon, polypropylene carbonate.
Further, the lithium salts is selected from lithium perchlorate, hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate, double oxalic acid
At least one of lithium borate, trifluoromethyl sulfonic acid lithium, bis- (trifluoromethane sulfonic acid) imine lithiums, bis- (fluorine sulphonyl) imine lithiums.
Further, the ingredient of the three-dimensional porous inorganic network of the lithium lanthanum zirconium oxygen is Li7-3xLa3Zr2MxO12Or Li7- xLa3Zr2-xMxO12, wherein M=Ta, Nb, Sb, Si, In, Ge, Ga, Al, Mo, 0≤x≤1.
A kind of preparation method of above-mentioned lithium lanthanum zirconium oxygen solid electrolyte absorbs precursor solution using template, to absorption
The template of precursor solution obtains lithium lanthanum zirconium oxygen three-dimensional porous network after being heat-treated, and passes through the dense of control precursor solution
Degree, heat treatment temperature and time, obtain the lithium lanthanum zirconium oxygen three-dimensional porous network film with mechanical property, specifically, include with
Lower step:
S1, lithium lanthanum zirconium oxygen precursor solution is prepared；
S2, template is soaked in lithium lanthanum zirconium oxygen precursor solution, takes out drying；
S3, the template after drying is heat-treated, obtains the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen；
S4, polymer and lithium salts are dissolved in organic solvent, are uniformly mixing to obtain mixed solution；
S5, the mixed solution of S4 is dropped evenly in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen, is then dried, repeat to be added dropwise
And drying, obtain composite membrane；
S6, the moisture for removing composite membrane and solvent (such as composite membrane being placed in Minton dryer dry), obtain lithium
Lanthanum zirconium oxygen solid electrolyte.
Further, the lithium lanthanum zirconium oxygen precursor solution is dissolved in water by the salt of lithium salts, lanthanum salt, zirconates, doped chemical
It is prepared.
Further, the doped chemical is Ta, Nb, Sb, Si, In, Ge, Ga, Al or Mo.
Further, the lithium salts is nitrate, acetate or the carbonate of lithium, and concentration is 30~50g/L；The lanthanum salt
For the nitrate, acetate or carbonate of lanthanum, concentration is 90~110g/L；The zirconates is zirconyl nitrate, zirconium oxychloride, nitric acid
Zirconium, acetic acid zirconium or zirconium sulfate, concentration are 25~55g/L；The salt of the doped chemical be the oxide of doped chemical, nitrate,
Chlorate, acetate, oxalates or carbonate, concentration are 2~45g/L.
S1 specifically: according to the stoichiometric ratio of lithium lanthanum zirconium oxygen, lithium, lanthanum, zirconium and the corresponding salt of doped chemical and water are mixed
It closes, obtains lithium lanthanum zirconium oxygen precursor solution after stirring and dissolving.
S2 specifically: by area be 400cm2Template is cut into 5 × 5cm2After be completely immersed in lithium lanthanum zirconium oxygen precursor solution
5~8h impregnates rear pattern plate and dries at 60~80 DEG C.
Further, the template is selected from dust-free paper, filter paper, lens wiping paper, bacteria cellulose.
Further, the temperature of the heat treatment be 700~900 DEG C, heating rate be 3~5 DEG C/min, heat treatment when
Between be 1~3h；The lithium salts is 10~35% in the mass percent of mixed solution, preferably 13.88wt%.
A kind of lithium ion battery, including cathode, anode, electrolyte, wherein the electrolyte is solid for above-mentioned lithium lanthanum zirconium oxygen
State electrolyte.Anode includes positive electrode active materials, binder and conductive additive；The positive electrode active materials are cobalt acid lithium, phosphorus
Sour iron lithium, lithium ferric manganese phosphate, LiMn2O4, nickel ion doped, lithium-rich manganese-based, ternary material, sulphur, sulfur compound, ferric sulfate lithium, lithium from
Sub- fluorophosphate, lithium vanadium fluorophosphate, lithium manganese oxide or conducting polymer；The binder is polyethylene glycol oxide, polypropylene
Nitrile, Kynoar, polymethyl methacrylate, polypropylene oxide, polyvinylpyrrolidone, Vingon or its derivative
Object；The negative electrode material is lithium metal, lithium metal alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, carbon-silicon composite material, carbon
Germanium composite material or metal lithium nitride.
The invention has the following advantages:
The present invention absorbs lithium lanthanum zirconium oxygen precursor solution using template, by being dried to obtain containing lithium lanthanum zirconium oxygen presoma
Template obtains the cubic phase lithium lanthanum zirconium oxygen three-dimensional porous network film with certain mechanical properties after being heat-treated.This method behaviour
Make simply, raw material is easy to get, at low cost, it can be achieved that large-scale production.By the method preparation lanthanum zirconium oxygen three-dimensional porous network film with
Polymer, lithium salts are compound to obtain composite solid electrolyte, and wherein lithium lanthanum zirconium oxygen three-dimensional porous network provides continuous lithium ion
Transmission channel keeps ionic conductivity higher.Meanwhile polymeric matrix provides certain flexibility for composite solid electrolyte, and lithium
The three-dimensional porous inorganic network of lanthanum zirconium oxygen provides certain mechanical strength for composite solid electrolyte；It is able to suppress the life of Li dendrite
It is long, improve the high-temperature behavior and safety of battery.To optimization and improve solid electrolyte and interelectrode interface compatibility
And stability, the solid lithium battery thus formed have that stable cycle performance, high rate performance are high, interface impedance is low, stability
Good advantage.
Detailed description of the invention
Fig. 1 is the XRD diagram of the 1 three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen of embodiment；
Fig. 2 is the SEM figure of the 1 three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen of embodiment；
Fig. 3 is the SEM figure of 1 lithium lanthanum zirconium oxygen solid electrolyte of embodiment；
Fig. 4 is the linear sweep voltammetry curve of 1 lithium lanthanum zirconium oxygen solid electrolyte of embodiment；
Fig. 5 is the charge-discharge performance figure of 1 solid lithium battery of embodiment.
Specific embodiment
The present invention is described further combined with specific embodiments below.
Embodiment 1
Lithium lanthanum zirconium oxygen solid electrolyte, consisting of: 63.56wt% polymer, 10.24wt% lithium salts and 26.20wt%
The three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen.
S1, lithium lanthanum zirconium oxygen precursor solution is prepared: by 0.9526g lithium nitrate, 2.598g lanthanum nitrate hexahydrate, 0.924g nitric acid
Oxygen zirconium, nine water aluminum nitrate of 0.18g are dissolved in 25mL deionized water, are stirred at room temperature 3 hours, are obtained
Li6.28La3Zr2Al0.24O12Precursor solution；
S2, by area be 400cm2Dust-free paper is cut into 5 × 5cm2After be completely immersed in 6h in lithium lanthanum zirconium oxygen precursor solution,
Rear pattern plate is impregnated to dry at 70 DEG C；
S3, by 5 × 5cm after drying2Dust-free paper 850 DEG C of heat treatment 2h, 5 DEG C/min of heating rate in Muffle furnace are obtained
To the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen；It carries out XRD object to it mutually to detect, as a result as shown in Figure 1, upper graph is logical in figure
The XRD spectrum for the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen that template obtains is crossed, lower surface curve is cubic phase lithium lanthanum zirconium oxygen standard x RD
Spectral line (ICSD-261302) illustrates the Li that cubic phase has been prepared by template6.28La3Zr2Al0.24O12；Scanning electron microscope is such as
Shown in Fig. 2, enlarged drawing, which is shown, has porous structure, illustrates the lithium lanthanum zirconium oxygen that tridimensional network has been obtained by template；
S4,0.132g polyethylene glycol oxide (molecular weight 900000) and 0.0213g lithium perchlorate (wherein polyoxyethylene groups are taken
With Li+Molar ratio is 15, i.e. EO/Li+=15) it is dissolved in 3mL acetonitrile, stirs 12h, obtain uniform mixed solution；
S5, the mixed solution of S4 is dropped evenly in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen, after be put into convection oven 70
DEG C drying repeats to be added dropwise and dry, fully enters mixed solution in porous, inorganic network, obtain composite membrane；
S6, composite membrane is transferred to 55 DEG C of dryings in vacuum oven, and for 24 hours, removal solvent and moisture obtain lithium lanthanum zirconium oxygen
Solid electrolyte PEO15-LiClO4-LLZAO。
Its scanning electron microscope is as shown in figure 3, polymer is uniformly compound with the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen and do not break
The three-dimensional structure of bad lithium lanthanum zirconium oxygen.
Through detecting, the solid electrolyte of the present embodiment is 2.25 × 10 in 30 DEG C of ionic conductivity-5S/cm；Non- complex lithium
The PEO of the three-dimensional porous inorganic network of lanthanum zirconium oxygen15-LiClO4The ionic conductivity that 30 DEG C of solid polyelectrolyte be 7.33 ×
10-7S/cm；The conductivity of the present embodiment can improve 30.7 times.
The linear sweep voltammetry curve of lithium lanthanum zirconium oxygen solid electrolyte is Fig. 4, and electrochemical stability window reaches 5V, illustrates electricity
The electrochemical stability for solving matter is good.
Solid electrolyte is assembled into solid lithium battery: by 0.07g iron phosphate serving as positive active material, 0.02g
Super P, 0.01g Kynoar are placed in mortar, and N-Methyl pyrrolidone is added dropwise and modulates anode sizing agent；It will modulate just
Pole slurry is coated on aluminium foil using scraper, first 60 DEG C of dry out solvent, rear 110 DEG C of vacuum drying 12h；Electrode slice is rushed after drying
Be pressed into required size, after be transferred in glove box；Using lithium metal as cathode, lithium lanthanum zirconium oxygen solid electrolyte membrane is electrolyte, group
Dress up CR2032 button cell.
Constant current charge-discharge performance is carried out in Neware battery test system (Xin Wei Enertech Co., Ltd., Shenzhen)
Test, charging and discharging currents density are 0.22mA/cm2, charge and discharge blanking voltage is 2.5~4V (vs.Li/Li+), test temperature 60
DEG C, the charge-discharge performance of solid lithium battery as shown in figure 5, upper graph represents coulombic efficiency, put by lower surface curve representative
Electric specific capacity, first circle specific discharge capacity reach 143.8mAh/g, and specific capacity keeps 86% after stablizing 200 circle of circulation, illustrate with lithium lanthanum
Zirconium oxygen composite solid electrolyte is that the all-solid-state battery of electrolyte has preferable specific capacity and cyclical stability.
Embodiment 2
Lithium lanthanum zirconium oxygen solid electrolyte, consisting of: 75wt% polymer, 10wt% lithium salts and 15wt% lithium lanthanum zirconium oxygen three
Tie up porous, inorganic network.
Lithium lanthanum zirconium oxygen solid electrolyte is prepared according to the following steps:
S1, lithium lanthanum zirconium oxygen precursor solution is prepared: by 0.834g lithium nitrate, 2.598g lanthanum nitrate hexahydrate, eight water of 1.289g
Conjunction zirconium oxychloride, 0.176g gallium trichloride are dissolved in 25mL deionized water, are stirred at room temperature 3 hours, are obtained
Li5.5La3Zr2Ga0.5O12Precursor solution；Nitric acid lithium concentration is 33.36g/L；Lanthanum nitrate hexahydrate concentration is 103.92g/L；
Eight hydration zirconium oxychloride concentration are 51.56g/L；Gallium trichloride concentration is 7.04g/L；
S2, by area be 400cm2Lens wiping paper is cut into 5 × 5cm2After be completely immersed in 6h in lithium lanthanum zirconium oxygen precursor solution,
Rear pattern plate is impregnated to dry at 70 DEG C；
S3, by the lens wiping paper after drying, 900 DEG C of heat treatments 1h, 3 DEG C/min of heating rate obtain lithium lanthanum zirconium in Muffle furnace
The three-dimensional porous inorganic network of oxygen；
S4,0.2g Kynoar and 0.027g trifluoromethyl sulfonic acid lithium are dissolved in 3mL N-Methyl pyrrolidone, are stirred
12h is mixed, uniform mixed solution is obtained；
S5, the mixed solution of S4 is dropped evenly in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen, after be put into convection oven 70
DEG C drying repeats to be added dropwise and dry, fully enters mixed solution in porous, inorganic network, obtain composite membrane；
S6, composite membrane is transferred to 100 DEG C of dry 12h in vacuum oven, removes solvent and moisture, obtains lithium lanthanum zirconium oxygen
Solid electrolyte PVDF-LiTf-LLZGO.
Through detecting, the solid electrolyte of the present embodiment is 2.52 × 10 in 30 DEG C of ionic conductivity-5S/cm；Non- complex lithium
30 DEG C of PVDF-LiTf solid polyelectrolyte of ionic conductivity of the three-dimensional porous inorganic network of lanthanum zirconium oxygen is 8.45 × 10- 7S/cm；The conductivity of the present embodiment can improve 29.8 times.
Embodiment 3
Lithium lanthanum zirconium oxygen solid electrolyte, consisting of: 60wt% polymer, 10wt% lithium salts and 30wt% lithium lanthanum zirconium oxygen three
Tie up porous, inorganic network.
Lithium lanthanum zirconium oxygen solid electrolyte is prepared according to the following steps:
S1, prepare lithium lanthanum zirconium oxygen precursor solution: by 0.944g lithium acetate, 1.896g lanthanum acetate, 0.982g acetic acid zirconium,
0.358g tantalic chloride is dissolved in 25mL deionized water, is stirred at room temperature 3 hours, is obtained Li6.5La3Zr1.5Ta0.5O12's
Precursor solution；Acetic acid lithium concentration is 37.76g/L；Acetic acid la concn is 75.84g/L；Acetic acid zirconium concentration is 39.28g/L；Five
Tantalic chloride concentration is 14.32g/L；
S2, by area be 400cm2Filter paper is cut into 5 × 5cm2After be completely immersed in 6h in lithium lanthanum zirconium oxygen precursor solution, soak
Rear pattern plate is steeped to dry at 60 DEG C；
S3, by the filter paper after drying in Muffle furnace 700 DEG C of heat treatments 3h, 5 DEG C/min of heating rate, obtain lithium lanthanum zirconium oxygen
Three-dimensional porous inorganic network；
S4, bis- (trifluoromethane sulfonic acid) imine lithiums of 0.08g polypropylene oxide and 0.013g are dissolved in 3mL acetonitrile, are stirred
12h obtains uniform mixed solution；
S5, the mixed solution of S4 is dropped evenly in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen, after be put into convection oven 70
DEG C drying repeats to be added dropwise and dry, fully enters mixed solution in porous, inorganic network, obtain composite membrane；
S6, composite membrane is transferred to 55 DEG C of dryings in vacuum oven, and for 24 hours, removal solvent and moisture obtain lithium lanthanum zirconium oxygen
Solid electrolyte PPO-LiTFSI-LLZTO.
Through detecting, the solid electrolyte of the present embodiment is 2.0 × 10 in 30 DEG C of ionic conductivity-5S/cm；Non- complex lithium
30 DEG C of PPO-LiTFSI solid polyelectrolyte of ionic conductivity of the three-dimensional porous inorganic network of lanthanum zirconium oxygen is 8.0 × 10- 7S/cm；The conductivity of the present embodiment can improve 25 times.
Embodiment 4
Lithium lanthanum zirconium oxygen solid electrolyte, consisting of: 60wt% polymer, 15wt% lithium salts and 25wt% lithium lanthanum zirconium oxygen three
Tie up porous, inorganic network.
Lithium lanthanum zirconium oxygen solid electrolyte is prepared according to the following steps:
S1, lithium lanthanum zirconium oxygen precursor solution is prepared: by 1.0618g lithium nitrate, 2.598g lanthanum nitrate hexahydrate, 0.924g nitric acid
Oxygen zirconium is dissolved in 25mL deionized water, is stirred at room temperature 3 hours, is obtained Li7La3Zr2O12Precursor solution；Lithium nitrate
Concentration is 42.47g/L；Lanthanum nitrate hexahydrate concentration is 103.92g/L；Zirconyl nitrate concentration is 36.96g/L；
S2, by area be 400cm2Bacteria cellulose is cut into 5 × 5cm2After be completely immersed in lithium lanthanum zirconium oxygen precursor solution
5h impregnates rear pattern plate and dries at 60 DEG C；
S3, by the bacteria cellulose heat after drying, 850 DEG C of heat treatment 2h, 5 DEG C/min of heating rate are obtained in Muffle furnace
The three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen；
S4, bis- (fluorine sulphonyl) imine lithiums of 0.091g polyacrylonitrile and 0.023g are dissolved in 3mL dimethyl base amide, are stirred
12h obtains uniform mixed solution；
S5, the mixed solution of S4 is dropped evenly in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen, after be put into convection oven 80
DEG C drying repeats to be added dropwise and dry, fully enters mixed solution in porous, inorganic network, obtain composite membrane；
S6, composite membrane is transferred to 100 DEG C of dryings in vacuum oven, and for 24 hours, removal solvent and moisture obtain lithium lanthanum zirconium oxygen
Solid electrolyte PAN-LiFSI-LLZO.
Through detecting, the solid electrolyte of the present embodiment is 1.2 × 10 in 30 DEG C of ionic conductivity-5S/cm；Non- complex lithium
30 DEG C of PAN-LiFSI solid polyelectrolyte of ionic conductivity of the three-dimensional porous inorganic network of lanthanum zirconium oxygen is 4.31 × 10- 7S/cm；The conductivity of the present embodiment can improve 27.8 times.
Embodiment 5
Lithium lanthanum zirconium oxygen solid electrolyte, consisting of: 70wt% polymer, 10wt% lithium salts and 20wt% lithium lanthanum zirconium oxygen three
Tie up porous, inorganic network.
Lithium lanthanum zirconium oxygen solid electrolyte is prepared according to the following steps:
S1, lithium lanthanum zirconium oxygen precursor solution is prepared: by 0.91g lithium nitrate, 2.598g lanthanum nitrate hexahydrate, 0.645g Nitric Acid Oxidation
Zirconium, 1.076g niobium oxalate are dissolved in 25mL deionized water, are stirred at room temperature 3 hours, are obtained Li6La3ZrNbO12Forerunner
Liquid solution；Nitric acid lithium concentration is 36.3g/L；Lanthanum nitrate hexahydrate concentration is 103.92g/L；Zirconyl nitrate concentration is 25.8g/L；Grass
Sour niobium concentration is 43.04g/L；
S2, by area be 400cm2Dust-free paper is cut into 5 × 5cm2After be completely immersed in 6h in lithium lanthanum zirconium oxygen precursor solution,
Rear pattern plate is impregnated to dry at 70 DEG C；
S3, by 5 × 5cm after drying2Dust-free paper 850 DEG C of heat treatment 2h, 5 DEG C/min of heating rate in Muffle furnace are obtained
To the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen；
S4, it takes 0.14g polymethyl methacrylate and 0.02g lithium hexafluoro phosphate to be dissolved in 3mL tetrahydrofuran, stirs 12h,
Obtain uniform mixed solution；
S5, the mixed solution of S4 is dropped evenly in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen, after be put into convection oven 50
DEG C drying repeats to be added dropwise and dry, fully enters mixed solution in porous, inorganic network, obtain composite membrane；
S6, composite membrane is transferred to 80 DEG C of dryings in vacuum oven, and for 24 hours, removal solvent and moisture obtain lithium lanthanum zirconium oxygen
Solid electrolyte PMMA-LiPF6-LLZNO。
Through detecting, the solid electrolyte of the present embodiment is 4.1 × 10 in 30 DEG C of ionic conductivity-7S/cm；Non- complex lithium
The PMMA-LiPF of the three-dimensional porous inorganic network of lanthanum zirconium oxygen6The ionic conductivity that 30 DEG C of solid polyelectrolyte is 2.67 × 10- 8S/cm；The conductivity of the present embodiment can improve 15.4 times.
Embodiment 6
Lithium lanthanum zirconium oxygen solid electrolyte, consisting of: 67wt% polymer, 8wt% lithium salts and 25wt% lithium lanthanum zirconium oxygen three
Tie up porous, inorganic network.
Lithium lanthanum zirconium oxygen solid electrolyte is prepared according to the following steps:
S1, prepare lithium lanthanum zirconium oxygen precursor solution: by 0.958g lithium acetate, 1.896g lanthanum acetate, 1.179g acetic acid zirconium,
0.065g molybdic acid is dissolved in 25mL deionized water, is stirred at room temperature 3 hours, is obtained Li6.6La3Zr1.8Mo0.2O12Forerunner
Liquid solution；Acetic acid lithium concentration is 38.32g/L；Acetic acid la concn is 75.84g/L；Acetic acid zirconium concentration is 47.16g/L；Molybdic acid is dense
Degree is 2.6g/L；
S2, by area be 400cm2Bacteria cellulose is cut into 5 × 5cm2After be completely immersed in lithium lanthanum zirconium oxygen precursor solution
5h impregnates rear pattern plate and dries at 60 DEG C；
S3, by the bacteria cellulose heat after drying, 850 DEG C of heat treatment 2h, 5 DEG C/min of heating rate are obtained in Muffle furnace
The three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen；
S4, bis- (trifluoromethane sulfonic acid) imine lithiums of 0.107g polypropylene carbonate and 0.013g are dissolved in 3mL acetonitrile, are stirred
12h is mixed, uniform mixed solution is obtained；
S5, the mixed solution of S4 is dropped evenly in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen, after be put into convection oven 80
DEG C drying repeats to be added dropwise and dry, fully enters mixed solution in porous, inorganic network, obtain composite membrane；
S6, composite membrane is transferred to 100 DEG C of dryings in vacuum oven, and for 24 hours, removal solvent and moisture obtain lithium lanthanum zirconium oxygen
Solid electrolyte PPC-LiTFSI-LLZMO.
Through detecting, the solid electrolyte of the present embodiment is 3 × 10 in 30 DEG C of ionic conductivity-4S/cm；Non- complex lithium lanthanum
30 DEG C of PPC-LiTFSI solid polyelectrolyte of ionic conductivity of the three-dimensional porous inorganic network of zirconium oxygen is 9.2 × 10-6S/
cm；The conductivity of the present embodiment can improve 32.6 times.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Belong to those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, all answers
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
Claims (10)
1. a kind of lithium lanthanum zirconium oxygen solid electrolyte, which is characterized in that including 60~75wt% polymer, 8~15wt% lithium salts and
The three-dimensional porous inorganic network of 15~30wt% lithium lanthanum zirconium oxygen, the polymer in situ are compound in the three-dimensional porous inorganic net of lithium lanthanum zirconium oxygen
Network.
2. lithium lanthanum zirconium oxygen solid electrolyte according to claim 1, which is characterized in that the polymer is selected from polyoxyethylene
Alkene, polyacrylonitrile, Kynoar, polymethyl methacrylate, polypropylene oxide, polyvinylpyrrolidone, Vingon,
At least one of polypropylene carbonate.
3. lithium lanthanum zirconium oxygen solid electrolyte according to claim 1, which is characterized in that the lithium salts be selected from lithium perchlorate,
Hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate, di-oxalate lithium borate, trifluoromethyl sulfonic acid lithium, bis- (trifluoromethane sulfonic acids)
At least one of imine lithium, bis- (fluorine sulphonyl) imine lithiums.
4. lithium lanthanum zirconium oxygen solid electrolyte according to claim 1, which is characterized in that the three-dimensional porous nothing of the lithium lanthanum zirconium oxygen
The ingredient of machine network is Li7-3xLa3Zr2MxO12Or Li7-xLa3Zr2-xMxO12, wherein M=Ta, Nb, Sb, Si, In, Ge, Ga,
Al, Mo, 0≤x≤1.
5. a kind of preparation method of the described in any item lithium lanthanum zirconium oxygen solid electrolytes of Claims 1 to 4, which is characterized in that packet
Include following steps:
S1, lithium lanthanum zirconium oxygen precursor solution is prepared；
S2, template is soaked in lithium lanthanum zirconium oxygen precursor solution, takes out drying；
S3, the template after drying is heat-treated, obtains the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen；
S4, polymer and lithium salts are dissolved in organic solvent, are uniformly mixing to obtain mixed solution；
S5, the mixed solution of S4 is dropped evenly in the three-dimensional porous inorganic network of lithium lanthanum zirconium oxygen, is then dried, repeat to be added dropwise and done
It is dry, obtain composite membrane；
S6, the moisture and solvent for removing composite membrane, obtain lithium lanthanum zirconium oxygen solid electrolyte.
6. according to the method described in claim 5, it is characterized in that, the lithium lanthanum zirconium oxygen precursor solution is by lithium salts, lanthanum salt, zirconium
Salt, doped chemical salt be dissolved in water and be prepared；The doped chemical is Ta, Nb, Sb, Si, In, Ge, Ga, Al or Mo.
7. according to the method described in claim 6, it is characterized in that, the lithium salts be lithium nitrate, acetate or carbonate,
Concentration is 30~50g/L；The lanthanum salt is nitrate, acetate or the carbonate of lanthanum, and concentration is 90~110g/L；The zirconates
For zirconyl nitrate, zirconium oxychloride, zirconium nitrate, acetic acid zirconium or zirconium sulfate, concentration is 25~55g/L；The salt of the doped chemical is
Oxide, nitrate, chlorate, acetate, oxalates or the carbonate of doped chemical, concentration are 2~45g/L.
8. according to the method described in claim 5, it is characterized in that, the template is selected from dust-free paper, filter paper, lens wiping paper, bacterium
Cellulose.
9. according to the method described in claim 5, it is characterized in that, the temperature of the heat treatment be 700~900 DEG C, heat treatment
Time be 1~3h；The lithium salts is 10~35% in the mass percent of mixed solution.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes cathode, anode, electrolyte, wherein described
Electrolyte is the described in any item lithium lanthanum zirconium oxygen solid electrolytes of Claims 1 to 4.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466239A (en) * | 2014-11-27 | 2015-03-25 | 中国科学院物理研究所 | Lithium-enriched anti-perovskite sulfides, solid electrolyte material containing lithium-enriched anti-perovskite sulfides and application of solid electrolyte material |
| CN106785009A (en) * | 2016-12-09 | 2017-05-31 | 北京科技大学 | A kind of all solid state composite electrolyte of organic-inorganic and its methods for making and using same |
| CN108987798A (en) * | 2018-06-22 | 2018-12-11 | 清华大学深圳研究生院 | A kind of integration all solid lithium metal battery |
| CN108987800A (en) * | 2018-07-24 | 2018-12-11 | 中国电子新能源（武汉）研究院有限责任公司 | Solid electrolyte and preparation method thereof and solid state battery containing the solid electrolyte |
| JP2018206486A (en) * | 2017-05-30 | 2018-12-27 | 凸版印刷株式会社 | Laminate green sheet, all-solid secondary battery and manufacturing method thereof |
-
2019
- 2019-01-04 CN CN201910006196.8A patent/CN109818051B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466239A (en) * | 2014-11-27 | 2015-03-25 | 中国科学院物理研究所 | Lithium-enriched anti-perovskite sulfides, solid electrolyte material containing lithium-enriched anti-perovskite sulfides and application of solid electrolyte material |
| CN106785009A (en) * | 2016-12-09 | 2017-05-31 | 北京科技大学 | A kind of all solid state composite electrolyte of organic-inorganic and its methods for making and using same |
| JP2018206486A (en) * | 2017-05-30 | 2018-12-27 | 凸版印刷株式会社 | Laminate green sheet, all-solid secondary battery and manufacturing method thereof |
| CN108987798A (en) * | 2018-06-22 | 2018-12-11 | 清华大学深圳研究生院 | A kind of integration all solid lithium metal battery |
| CN108987800A (en) * | 2018-07-24 | 2018-12-11 | 中国电子新能源（武汉）研究院有限责任公司 | Solid electrolyte and preparation method thereof and solid state battery containing the solid electrolyte |
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