CN101521296A - Composite solid electrolyte and preparation method thereof - Google Patents

Composite solid electrolyte and preparation method thereof Download PDF

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CN101521296A
CN101521296A CN200910080978A CN200910080978A CN101521296A CN 101521296 A CN101521296 A CN 101521296A CN 200910080978 A CN200910080978 A CN 200910080978A CN 200910080978 A CN200910080978 A CN 200910080978A CN 101521296 A CN101521296 A CN 101521296A
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solid electrolyte
metal oxide
nanoporous
composite solid
composite metal
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CN101521296B (en
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杨文胜
王立仕
王健
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Beijing University of Chemical Technology
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Abstract

The invention relates to a composite solid electrolyte and a preparation method thereof, which belongs to the technical field of lithium ion battery electrolyte materials and the preparation technology thereof. The composite solid electrolyte comprises polyethylene glycol oxide, lithium salt and nanometer multiporous spinel combined metal oxide. The preparation method comprises the steps: the nanometer multiporous spinel combined metal oxide is added into an acetonitrile solvent for ultrasonic dispersion; then, the polyethylene glycol oxide and the lithium salt are added into the mixture and are mixed at room temperature to obtain even and transparent viscous solution; the solution is poured into a polyfluortetraethylene mould protected by nitrogen to vaporize the acetonitrile solvent; and finally, the solution is dried in vacuum to obtain a composite solid electrolyte film containing the nanometer multiporous spinel combined metal oxide. The method uses the spinel combined metal oxide with the nanometer size and the multiporous structure as an additive to prepare the composite solid electrolyte which has high lithium ion transference number, high ionic conductivity, low interface resistance and good electrochemical stability. The composite solid electrolyte can be used for all solid state lithium ion batteries.

Description

A kind of composite solid electrolyte and preparation method thereof
Technical field
The invention belongs to lithium ion battery electrolyte materials and preparing technical field thereof, particularly relate to a kind of composite solid electrolyte and preparation method thereof, can be used for the composite solid electrolyte that contains the nanoporous spinel type composite metal oxide of all solid state lithium ion battery
Background technology
Since people such as Wright in 1973 find that first polyethylene glycol oxide (PEO) and alkali metal salt coordination have ionic conductivity, polyethylene glycol oxide-lithium salts (PEO-LiX) polymer electrolyte system is just with light weight, pollution-free, can replace the liquid electrolyte in traditional lithium ion battery and is subjected to extensive concern.But it is low that the PEO-LiX solid electrolyte of non-modified exists under the normal temperature ionic conductivity and lithium ion transference number, shortcomings such as electrochemical stability and bad mechanical property.Add inorganic material and can obtain composite solid electrolyte in the PEO-LiX polymer electrolyte system, its ionic conductivity, lithium ion transference number, electrochemical stability and mechanical performance etc. all can be improved by a relatively large margin.The inorganic material of adding mainly is divided into nano inorganic material and porous inorganic material two big classes at present.
At document (1) Nature, 1998,394, among the 456-458, people such as F.Croce are with nanometer Al 2O 3, TiO 2Particle is incorporated into PEO-LiClO 4In the system, utilize solution casting method to prepare composite solid electrolyte, its electrical conductivity at room temperature and high temperature lithium ion transference number compare PEO-LiClO 4Had to significantly improve, 30 ℃ of following ionic conductivities are from 10 -8S/cm brings up to 10 -5S/cm, 90 ℃ of following lithium ion transference numbers bring up to 0.6 from 0.2.
At document (2) Journal of Power Sources, 2006,156, among the 581-588, people such as Jingyu Xi join PEO-LiClO to the molecular sieve ZSM-5 with loose structure 4In the system, the electrical conductivity at room temperature of the composite solid electrolyte that is obtained and high temperature lithium ion transference number are than Polymer Electrolyte PEO-LiClO 4Had to significantly improve, 25 ℃ of following ionic conductivities are from 10 -8S/cm brings up to 10 -6S/cm, 90 ℃ of following lithium ion transference numbers bring up to 0.360 from 0.196, simultaneously this electrolyte also have good electrochemical stability and with the interface stability of lithium.
If add the inorganic material that has nano-scale and loose structure simultaneously to PEO-LiClO 4In the system, the composite solid electrolyte expection that is then obtained will have better performance, but bibliographical information is not seen in correlative study as yet.
Summary of the invention
The object of the present invention is to provide a kind of composite solid electrolyte and preparation method thereof.
The composite solid electrolyte that the present invention contains the nanoporous spinel type composite metal oxide is made up of polyethylene glycol oxide, lithium salts and nanoporous spinel type composite metal oxide, the mass fraction scope of each component in composite solid electrolyte is respectively 70.0～90.0%, 7.1～28.2% and 1.4～21.5%.Wherein the molecular weight of polyethylene glycol oxide is 1 * 10 5～1 * 10 6Lithium salts is LiClO 4, LiPF 6In any one; The nanoporous spinel type composite metal oxide is ZnAl 2O 4, its average particle size distribution scope is 30～70nm, the most probable pore size distribution range is 6～15nm.
Most probable is exactly the highest meaning of probability, and the most probable aperture is exactly the pore size that most probable occurs.
The preparation method and the processing step thereof of nanoporous spinel type composite metal oxide of the present invention are as follows:
According to the Zn/Al mol ratio be 2/1～4/1 and total concentration be [Zn 2+]+[Al 3+]=1.0～1.5mol/L takes by weighing Zn (NO 3) 26H 2O and Al (NO 3) 39H 2O is dissolved in and is mixed with salting liquid in the deionized water; According to [CO 3 2-]=2.0[Al 3+], [OH -]=1.6 ([Zn 2+]+[Al 3+]) take by weighing NaOH and NaCO 3Be made into and the isopyknic aqueous slkali of salting liquid.Pour into above-mentioned salting liquid and aqueous slkali in the colloid mill simultaneously, reacted 2～3 minutes down in 2000～4000 rev/mins rotating speeds, then white slurries are transferred in the there-necked flask in 60～90 ℃ of crystallization 4～6 hours, after repeatedly being 7～8 with the crystallization product suction filtration, with deionized water wash to pH value of filtrate, filter cake obtains zinc-aluminium di-hydroxyl composite metal oxidate presoma 60～90 ℃ of oven dryings 12～24 hours.Above-mentioned presoma is put into Muffle furnace, begin to be incubated 2～4 hours after speed with 6～12 ℃/min is warming up to 600～750 ℃ from room temperature, product of roasting takes out after cooling to room temperature with the furnace.According to the mass volume ratio of product of roasting and NaOH solution is 1/20～1/30 to take by weighing product of roasting and put into round-bottomed flask, make it to become uniform suspension-turbid liquid to concentrated NaOH solution that wherein adds 10mol/L and stirring, after reacting 48～72 hours under 50～80 ℃, centrifugation and washing are repeatedly, pH value to suspension-turbid liquid is 7～8, the solid precipitation that centrifugation is obtained is put into 60～90 ℃ dry 12～24 hours of drying box, obtains nanoporous spinel type composite metal oxide ZnAl 2O 4
The present invention contains nanoporous spinel type composite metal oxide ZnAl 2O 4Method for preparing composite solid electrolyte and processing step thereof as follows:
Take by weighing polyethylene glycol oxide, lithium salts and three kinds of materials of nanoporous spinel type composite metal oxide, the mass fraction that they account for three kinds of material gross masses is respectively 70.0～90.0%, and 7.1～28.2% and 1.4～21.5%.The nanoporous spinel type composite metal oxide of weighing was joined in the acetonitrile solvent that is equivalent to 10～15 times of three kinds of material gross masses ultrasonic dispersion 1～3 hour; the polyethylene glycol oxide and the lithium salts that add weighing then; stirring at room obtains the thick liquid of homogeneous transparent after 24～48 hours; this liquid is poured in the polytetrafluoroethylene mould of nitrogen protection; room temperature evaporation acetonitrile solvent 2～3 days; and then in 50 ℃ of vacuumizes 48～72 hours, obtaining thickness was the composite solid electrolyte film that contains the nanoporous spinel type composite metal oxide of 100～200 μ m.Wherein the molecular weight ranges of polyethylene glycol oxide is 1 * 10 5～1 * 10 6Lithium salts is LiClO 4, LiPF 6In any one; The nanoporous spinel type composite metal oxide is ZnAl 2O 4, its average particle size distribution scope is 30～70nm, the most probable pore size distribution range is 6～15nm.
Employing FDAC H-800 type transmission electron microscope characterizes composite metal oxide, measures its particle diameter.Adopt U.S. Quantachrome Autosorb-1 type to adsorb instrument automatically composite metal oxide is carried out cryogenic nitrogen aspiration-desorption test, determine the pore structure and the pore-size distribution (the results are shown in Figure 1) of composite metal oxide.
Composite solid electrolyte is sandwiched between the stainless steel substrate of two surface finish, adopts the German ZAHNERELEKTRIK IM6e of company type electrochemical workstation to carry out ac impedance measurement.According to formula σ=1/R bD/S calculates the room-temperature conductivity of composite solid electrolyte, and wherein σ is a conductivity, R bBe the resistance of composite solid electrolyte, d is the thickness of composite solid electrolyte, and S is the area of composite solid electrolyte, with PEO-LiClO 4Compare, the conductivity of composite solid electrolyte has had and has significantly improved (the results are shown in Figure 2).Assembling lithium/composite solid electrolyte/lithium button cell adopts the U.S. MSTAT4+ of Arbin company type constant current charge-discharge instrument record current-time (I-t) curve (see figure 3), adopts IM6e type electrochemical workstation to carry out the ac impedance measurement (see figure 4).According to formula t + = I s ( ΔV - I 0 R 0 ) I 0 ( ΔV - I s R s ) Calculate the lithium ion transference number of composite solid electrolyte, wherein t +Be lithium ion transference number, I 0Be initial current, I sBe steady-state current, R oBe initial resistance, R sBe steadying resistance, Δ V is the polarizing voltage that applies.With PEO-LiClO 4Compare, the lithium ion transference number of composite solid electrolyte has had significant raising, the results are shown in shown in the following table 1.
Table 1. lithium ion transference number
Figure A200910080978D00042
Figure A200910080978D00051
Adopt the resistance at IM6e type electrochemical workstation test compound solid electrolyte and lithium interface, with PEO-LiClO 4Compare, the resistance at composite solid electrolyte and lithium interface obviously reduces (the results are shown in Figure 5).Assembling lithium/composite solid electrolyte/steel disc button cell adopts IM6e type electrochemical workstation record linear scan volt-ampere curve, and sweep limits is open circuit voltage～6V (vs.Li +/ Li), with PEO-LiClO 4Compare, composite solid electrolyte has better electrochemical stability (the results are shown in Figure 6), and potential window can reach 5.5V (vs.Li +/ Li) more than.
Implementation result of the present invention and advantage are: the present invention will have the spinel type composite metal oxide ZnAl of nano-scale and loose structure simultaneously 2O 4Add PEO-LiClO to 4In the system, the composite solid electrolyte that is obtained has high-lithium ion transport number, high ionic conductivity, less interface resistance and good electrochemical stability.
Description of drawings
Fig. 1 is embodiment 1 nanoporous composite metal oxide ZnAl 2O 4Nitrogen adsorption desorption curve and graph of pore diameter distribution (interior figure).Abscissa is relative pressure (P/P o), ordinate is the adsorption desorption amount, unit is cubic centimetre/gram (cm 3/ g).Interior figure abscissa is a bore dia, and unit is nanometer (nm).
Fig. 2 is PEO-LiClO in embodiment 1 composite solid electrolyte and the Comparative Examples 1 4Ionic conductivity vary with temperature curve.The ionic conductivity of curve (a)-embodiment 1 composite solid electrolyte varies with temperature curve; PE0-LiClO in curve (b)-Comparative Examples 1 4Ionic conductivity vary with temperature curve.Abscissa is absolute temperature (1000/T), and unit is 1/ Kelvin (K -1); Ordinate is a conductivity, and unit is Siemens/cm (S/cm).
Fig. 3 is for after applying constant voltage, lithium/composite solid electrolyte of embodiment 1/lithium button cell time-the current density curve.Abscissa is the time, and unit is second (s); Ordinate is a current density, and unit is microampere/square centimeter (μ A/cm 2).
Fig. 4 for lithium/composite solid electrolyte/lithium button cell of embodiment 1 before applying constant voltage and reach AC impedance figure behind the steady-state current.Before the curve (a)-apply constant voltage, the AC impedance figure of lithium/composite solid electrolyte/lithium button cell.Curve (b)-lithium/composite solid electrolyte/lithium button cell reaches the AC impedance figure behind the steady-state current.Abscissa is a real part, and unit is ohm (Ω); Ordinate is an imaginary part, and unit is ohm (Ω).
Fig. 5 is PEO-LiClO in embodiment 1 composite solid electrolyte and the Comparative Examples 1 4Interface resistance with lithium.The interface resistance of curve (a)-embodiment 1 composite solid electrolyte and lithium; PEO-LiClO in curve (b)-Comparative Examples 1 4Interface resistance with lithium.Abscissa is a real part, and unit is ohm (Ω); Ordinate is an imaginary part, and unit is ohm (Ω).
Fig. 6 is PEO-LiClO in the composite solid electrolyte of embodiment 1 and the Comparative Examples 1 4The electric potential scanning curve.The electric potential scanning curve of curve (a)-embodiment 1 composite solid electrolyte; PEO-LiClO in curve (b)-Comparative Examples 1 4The electric potential scanning curve.Abscissa is the time, and unit is second (s); Ordinate is a current density, and unit is microampere/square centimeter (μ A/cm 2).
Embodiment
Embodiment 1:
According to the Zn/Al mol ratio be 3/1 and total concentration be [Zn 2+]+[Al 3+]=1.2mol/L takes by weighing Zn (NO 3) 26H 2O and Al (NO 3) 39H 2O is dissolved in and is mixed with salting liquid in the deionized water; According to [CO 3 2-]=2.0[Al 3+], [OH -]=1.6 ([Zn 2+]+[Al 3+]) take by weighing NaOH and NaCO 3Be made into and the isopyknic aqueous slkali of salting liquid.Pour into above-mentioned salting liquid and aqueous slkali in the colloid mill simultaneously, reacted 2 minutes down in 3000 rev/mins rotating speeds, then white slurries are transferred in the there-necked flask in 90 ℃ of crystallization 4 hours, with the crystallization product suction filtration, with deionized water wash repeatedly to the pH=7 of filtrate, filter cake obtains zinc-aluminium di-hydroxyl composite metal oxidate presoma 60 ℃ of oven dryings 12 hours.Above-mentioned presoma is put into Muffle furnace, from room temperature begin speed with 10 ℃/min be warming up to 700 ℃ after insulation 2 hours, product of roasting takes out after cooling to room temperature with the furnace.According to the mass volume ratio of product of roasting and NaOH solution is 1/20 to take by weighing product of roasting and put into round-bottomed flask, make it to become uniform suspension-turbid liquid to concentrated NaOH solution that wherein adds 10mol/L and stirring, after reacting 48 hours under 60 ℃, centrifugation and washing are repeatedly, pH value to suspension-turbid liquid is 7, the solid precipitation that centrifugation is obtained is put into 60 ℃ dry 12 hours of drying box, obtaining average grain diameter is 50nm, and the most probable aperture is the nanoporous spinel type composite metal oxide ZnAl of 7.8nm (Fig. 1) 2O 4
(molecular weight is 1 * 10 to take by weighing polyethylene glycol oxide 5), LiClO 4With nanoporous spinel-type ZnAl 2O 4Be respectively 0.500g, 0.075g, 0.040g.With the spinel-type ZnAl that takes by weighing 2O 4Join in the 7mL acetonitrile solvent ultrasonic dispersion 1 hour, and under stirring condition, added polyethylene glycol oxide and the LiClO that takes by weighing 4Stirring at room obtains the viscous solution of homogeneous transparent after 24 hours then, this solution is poured in the polytetrafluoroethylene mould that is subjected to nitrogen protection into evaporation acetonitrile solvent 2 days; and then in 50 ℃ of vacuumizes 48 hours, obtaining thickness at last was the translucent composite solid electrolyte film of 150 μ m.Then to prepared sample carry out ionic conductivity (Fig. 2), lithium ion transference number (Fig. 3, Fig. 4 and table 1), with the interface resistance (Fig. 5) of lithium and the test of electrochemical stability window (Fig. 6).Test result shows that this composite solid electrolyte and lithium have less interface resistance, has the electrochemical stability window of broad, and its room-temperature conductivity is 2.23 * 10 -6S/cm, 70 ℃ lithium ion transference number are 0.498.
Embodiment 2:
According to the Zn/Al mol ratio be 4/1 and total concentration be [Zn 2+]+[Al 3+]=1.0mol/L takes by weighing Zn (NO 3) 26H 2O and Al (NO 3) 39H 2O is dissolved in and is mixed with salting liquid in the deionized water; According to [CO 3 2-]=2.0[Al 3+], [OH -]=1.6 ([Zn 2+]+[Al 3+]) take by weighing NaOH and NaCO 3Be made into and the isopyknic aqueous slkali of salting liquid.Pour into above-mentioned salting liquid and aqueous slkali in the colloid mill simultaneously, reacted 3 minutes down in 2000 rev/mins rotating speeds, then white slurries are transferred in the there-necked flask in 80 ℃ of crystallization 5 hours, with the crystallization product suction filtration, with deionized water wash repeatedly to the pH=7 of filtrate, filter cake obtains zinc-aluminium di-hydroxyl composite metal oxidate presoma 80 ℃ of oven dryings 15 hours.Above-mentioned presoma is put into Muffle furnace, from room temperature begin speed with 12 ℃/min be warming up to 650 ℃ after insulation 3 hours, product of roasting takes out after cooling to room temperature with the furnace.According to the mass volume ratio of product of roasting and NaOH solution is 1/25 to take by weighing product of roasting and put into round-bottomed flask, make it to become uniform suspension-turbid liquid to concentrated NaOH solution that wherein adds 10mol/L and stirring, after reacting 60 hours under 60 ℃, centrifugation and washing are repeatedly, pH value to suspension-turbid liquid is 8, the solid precipitation that centrifugation is obtained is put into 80 ℃ dry 15 hours of drying box, obtaining average grain diameter is 40nm, and the most probable aperture is about the nanoporous spinel type composite metal oxide ZnAl of 7nm 2O 4
(molecular weight is 1 * 10 to take by weighing polyethylene glycol oxide 5), LiPF 6With nanoporous spinel-type ZnAl 2O 4Be respectively 0.500g, 0.200g, 0.010g.With the spinel-type ZnAl that takes by weighing 2O 4Joined in the 8mL acetonitrile solvent ultrasonic dispersion 1 hour, (molecular weight is 1 * 10 to add the polyethylene glycol oxide that takes by weighing under stirring condition 5) and LiPF 6, preparation process obtains the composite solid electrolyte film that thickness is about 200 μ m at last with embodiment 1.Then to prepared sample carry out ionic conductivity, lithium ion transference number, with the interface resistance of lithium and the test of electrochemical stability window.Test result shows that this composite solid electrolyte and lithium have less interface resistance, has the electrochemical stability window of broad, and its room-temperature conductivity is 1.08 * 10 -6S/cm, 70 ℃ lithium ion transference number are 0.287.
Embodiment 3:
According to the Zn/Al mol ratio be 2/1 and total concentration be [Zn 2+]+[Al 3+]=1.5mol/L takes by weighing Zn (NO 3) 26H 2O and Al (NO 3) 39H 2O is dissolved in and is mixed with salting liquid in the deionized water; According to [CO 3 2-]=2.0[Al 3+], [OH -]=1.6 ([Zn 2+]+[Al 3+]) take by weighing NaOH and NaCO 3Be made into and the isopyknic aqueous slkali of salting liquid.Pour into above-mentioned salting liquid and aqueous slkali in the colloid mill simultaneously, reacted 2 minutes down in 4000 rev/mins rotating speeds, then white slurries are transferred in the there-necked flask in 70 ℃ of crystallization 6 hours, with the crystallization product suction filtration, with deionized water wash repeatedly to the pH=8 of filtrate, filter cake obtains zinc-aluminium di-hydroxyl composite metal oxidate presoma 70 ℃ of oven dryings 12 hours.Above-mentioned presoma is put into Muffle furnace, from room temperature begin speed with 12 ℃/min be warming up to 750 ℃ after insulation 2 hours, product of roasting takes out after cooling to room temperature with the furnace.According to the mass volume ratio of product of roasting and NaOH solution is 1/20 to take by weighing product of roasting and put in the round-bottomed flask, make it to become uniform suspension-turbid liquid to concentrated NaOH solution that wherein adds 10mol/L and stirring, after reacting 48 hours under 70 ℃, centrifugation and washing are repeatedly, pH value to suspension-turbid liquid is 7, the solid precipitation that centrifugation is obtained is put into 70 ℃ dry 24 hours of drying box, obtaining average grain diameter is 70nm, and the most probable aperture is the nanoporous spinel type composite metal oxide ZnAl of 14nm 2O 4
(molecular weight is 1 * 10 to take by weighing polyethylene glycol oxide 6), LiClO 4With nanoporous spinel-type ZnAl 2O 4Be respectively 0.500g, 0.050g, 0.150g.With the spinel-type ZnAl that takes by weighing 2O 4Joined in the 8mL acetonitrile solvent ultrasonic dispersion 1 hour, (molecular weight is 1 * 10 to add the polyethylene glycol oxide that takes by weighing under stirring condition 6) and LiClO 4, preparation process obtains the composite solid electrolyte film that thickness is about 200 μ m at last with embodiment 1.Then to prepared sample carry out ionic conductivity, lithium ion transference number, with the interface resistance of lithium and the test of electrochemical stability window.Test result shows that this composite solid electrolyte and lithium have less interface resistance, has the electrochemical stability window of broad, and its room-temperature conductivity is 7.45 * 10 -7S/cm, 70 ℃ lithium ion transference number are 0.408.
Embodiment 4:
According to the Zn/Al mol ratio be 3/1 and total concentration be [Zn 2+]+[Al 3+]=1.0mol/L takes by weighing Zn (NO 3) 26H 2O and Al (NO 3) 39H 2O is dissolved in and is mixed with salting liquid in the deionized water; According to [CO 3 2-]=2.0[Al 3+], [OH -]=1.6 ([Zn 2+]+[Al 3+]) take by weighing NaOH and NaCO 3Be made into and the isopyknic aqueous slkali of salting liquid.Pour into above-mentioned salting liquid and aqueous slkali in the colloid mill simultaneously, reacted 3 minutes down in 3000 rev/mins rotating speeds, then white slurries are transferred in the there-necked flask in 60 ℃ of crystallization 6 hours, with the crystallization product suction filtration, with deionized water wash repeatedly to the pH=7 of filtrate, filter cake obtains zinc-aluminium di-hydroxyl composite metal oxidate presoma 60 ℃ of oven dryings 20 hours.Above-mentioned presoma is put into Muffle furnace, from room temperature begin speed with 6 ℃/min be warming up to 600 ℃ after insulation 4 hours, product of roasting takes out after cooling to room temperature with the furnace.According to the mass volume ratio of product of roasting and NaOH solution is 1/30 to take by weighing product of roasting and put into round-bottomed flask, make it to become uniform suspension-turbid liquid to concentrated NaOH solution that wherein adds 10mol/L and stirring, after reacting 72 hours under 80 ℃, centrifugation and washing are repeatedly, pH value to suspension-turbid liquid is 8, the solid precipitation that centrifugation is obtained is put into 80 ℃ dry 12 hours of drying box, obtaining average grain diameter is 30nm, and the most probable aperture is the nanoporous spinel type composite metal oxide ZnAl of 6.2nm 2O 4
(molecular weight is 1 * 10 to take by weighing polyethylene glycol oxide 6), LiPF 6With nanoporous spinel-type ZnAl 2O 4Be respectively 0.500g, 0.100g, 0.075g.With the spinel-type ZnAl that takes by weighing 2O 4Joined in the 8mL acetonitrile solvent ultrasonic dispersion 1 hour, (molecular weight is 1 * 10 to add the polyethylene glycol oxide that takes by weighing under stirring condition 6) and LiPF 6, preparation process obtains the composite solid electrolyte film that thickness is about 180 μ m at last with embodiment 1.Then to prepared sample carry out ionic conductivity, lithium ion transference number, with the interface resistance of lithium and the test of electrochemical stability window.Test result shows that this composite solid electrolyte and lithium have less interface resistance, has the electrochemical stability window of broad, and its room-temperature conductivity is 1.35 * 10 -6S/cm, 70 ℃ lithium ion transference number are 0.515.
Embodiment 5:
According to the Zn/Al mol ratio be 4/1 and total concentration be [Zn 2+]+[Al 3+]=1.2mol/L takes by weighing Zn (NO 3) 26H 2O and Al (NO 3) 39H 2O is dissolved in and is mixed with salting liquid in the deionized water; According to [CO 3 2-]=2.0[Al 3+], [OH -]=1.6 ([Zn 2+]+[Al 3+]) take by weighing NaOH and NaCO 3Be made into and the isopyknic aqueous slkali of salting liquid.Pour into above-mentioned salting liquid and aqueous slkali in the colloid mill simultaneously, reacted 2 minutes down in 4000 rev/mins rotating speeds, then white slurries are transferred in the there-necked flask in 90 ℃ of crystallization 4 hours, with the crystallization product suction filtration, with deionized water wash repeatedly to the pH=8 of filtrate, filter cake obtains zinc-aluminium di-hydroxyl composite metal oxidate presoma 60 ℃ of oven dryings 24 hours.Above-mentioned presoma is put into Muffle furnace, from room temperature begin speed with 8 ℃/min be warming up to 700 ℃ after insulation 3 hours, product of roasting takes out after cooling to room temperature with the furnace.According to the mass volume ratio of product of roasting and NaOH solution is 1/20 to take by weighing product of roasting and put into round-bottomed flask, make it to become uniform suspension-turbid liquid to concentrated NaOH solution that wherein adds 10mol/L and stirring, after reacting 72 hours under 50 ℃, centrifugation and washing are repeatedly, pH value to suspension-turbid liquid is 7, the solid precipitation that centrifugation is obtained is put into 90 ℃ dry 12 hours of drying box, obtaining average grain diameter is 45nm, and the most probable aperture is the nanoporous spinel type composite metal oxide ZnAl of 7.5nm 2O 4
(molecular weight is 1 * 10 to take by weighing polyethylene glycol oxide 5), LiClO 4With nanoporous spinel-type ZnAl 2O 4Be respectively 0.500g, 0.050g, 0.010g.With the spinel-type ZnAl that takes by weighing 2O 4Joined in the 7mL acetonitrile solvent ultrasonic dispersion 1 hour, (molecular weight is 1 * 10 to add the polyethylene glycol oxide that takes by weighing under stirring condition 5) and LiClO 4, preparation process obtains the composite solid electrolyte film that thickness is about 100 μ m at last with embodiment 1.Then to prepared sample carry out ionic conductivity, lithium ion transference number, with the interface resistance of lithium and the test of electrochemical stability window.Test result shows that this composite solid electrolyte and lithium have less interface resistance, has the electrochemical stability window of broad, and its room-temperature conductivity is 6.55 * 10 -7S/cm, 70 ℃ lithium ion transference number are 0.265.
Comparative Examples 1:
(molecular weight is 1 * 10 to take by weighing polyethylene glycol oxide 5), LiClO 4Be respectively 0.500g, 0.075g.With the LiClO that takes by weighing 4With the dissolving of 8mL acetonitrile solvent, (molecular weight is 1 * 10 to add the polyethylene glycol oxide that takes by weighing under stirring condition 5), preparation process has prepared the PEO that is about 120 μ m at last with embodiment 1 16-LiClO 4Translucent solid electrolyte film.Then to prepared sample carry out ionic conductivity (Fig. 2), lithium ion transference number (table 1), with the interface resistance (Fig. 5) of lithium and the test of electrochemical stability window (Fig. 6).Test result shows that this all solid state electrolyte and lithium have bigger interface resistance, has narrower electrochemical stability window, and its room-temperature conductivity is 6.08 * 10 -8S/cm, 70 ℃ lithium ion transference number are 0.191.

Claims (4)

1. composite solid electrolyte, it is characterized in that: this composite solid electrolyte is made up of polyethylene glycol oxide, lithium salts and nanoporous spinel type composite metal oxide, and the mass fraction of each component is: polyethylene glycol oxide: 70.0～90.0%, lithium salts: 7.1～28.2%, the nanoporous spinel type composite metal oxide 1.4～21.5%; Wherein the molecular weight of polyethylene glycol oxide is 1 * 10 5～1 * 10 6Lithium salts is LiClO 4, LiPF 6In any one; The nanoporous spinel type composite metal oxide is ZnAl 2O 4, its average particle size distribution scope is 30～70nm, the most probable pore size distribution range is 6～15nm.
2. a method for preparing the described composite solid electrolyte of claim 1 is characterized in that, processing step is:
Press polyethylene glycol oxide: 70.0～90.0%; lithium salts: 7.1～28.2%; the mass fraction of nanoporous spinel type composite metal oxide 1.4～21.5% takes by weighing this three kinds of materials; the nanoporous spinel type composite metal oxide of weighing was joined in the acetonitrile solvent that is equivalent to 10～15 times of three kinds of material gross masses ultrasonic dispersion 1～3 hour; the polyethylene glycol oxide and the lithium salts that add weighing then; stirring at room obtains the thick liquid of homogeneous transparent after 24～48 hours; this liquid is poured in the polytetrafluoroethylene mould of nitrogen protection; room temperature evaporation acetonitrile solvent 2～3 days; and then in 50 ℃ of vacuumizes 48～72 hours, obtaining thickness was the composite solid electrolyte film that contains the nanoporous spinel type composite metal oxide of 100～200 μ m.
3. method according to claim 2 is characterized in that, the molecular weight ranges of polyethylene glycol oxide is 1 * 10 5～1 * 10 6Lithium salts is LiCl0 4, LiPF 6In any one; The nanoporous spinel type composite metal oxide is ZnAl 2O 4, its average particle size distribution scope is 30～70nm, the most probable pore size distribution range is 6～15nm.
4. according to claim 2 or 3 described methods, it is characterized in that the processing step of described nanoporous spinel type composite metal oxide preparation is:
According to the Zn/Aminl.gif mol ratio be 2/1～4/1 and total concentration be [Zn 2+]+[Al 3+]=1.0～1.5mol/L takes by weighing Zn (NO 3) 26H 2O and Al (NO 3) 39H 2O is dissolved in and is mixed with salting liquid in the deionized water; According to [CO 3 2-]=2.0[Al 3+], [OH -]=1.6 ([Zn 2+]+[Al 3+]) take by weighing NaOH and NaCO 3Be made into and the isopyknic aqueous slkali of salting liquid; Pour into above-mentioned salting liquid and aqueous slkali in the colloid mill simultaneously, reacted 2～3 minutes down in 2000～4000 rev/mins rotating speeds, then white slurries are transferred in the there-necked flask in 60～90 ℃ of crystallization 4～6 hours, after repeatedly being 7～8 with the crystallization product suction filtration, with deionized water wash to pH value of filtrate, filter cake obtains zinc-aluminium di-hydroxyl composite metal oxidate presoma 60～90 ℃ of oven dryings 12～24 hours; Above-mentioned presoma is put into Muffle furnace, begin to be incubated 2～4 hours after speed with 6～12 ℃/min is warming up to 600～750 ℃ from room temperature, product of roasting takes out after cooling to room temperature with the furnace; According to the mass volume ratio of product of roasting and NaOH solution is 1/20～1/30 to take by weighing product of roasting and put into round-bottomed flask, make it to become uniform suspension-turbid liquid to concentrated NaOH solution that wherein adds 10mol/L and stirring, after reacting 48～72 hours under 50～80 ℃, centrifugation and washing are repeatedly, pH value to suspension-turbid liquid is 7～8, the solid precipitation that centrifugation is obtained is put into 60～90 ℃ dry 12～24 hours of drying box, obtains nanoporous spinel type composite metal oxide ZnAl 2O 4
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