CN110504481A - Salt mixes polymer-type composite solid electrolyte and preparation method thereof, lithium battery - Google Patents
Salt mixes polymer-type composite solid electrolyte and preparation method thereof, lithium battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The present invention is suitable for field of lithium ion battery material, provides a kind of salt and mixes polymer-type composite solid electrolyte and preparation method thereof, lithium battery, wherein it includes: ceramic nano line, polymeric matrix and lithium salts that the salt, which mixes polymer-type composite solid electrolyte,；The ratio of polymer and lithium salts in the polymeric matrix is (4~11): 1；The total mass ratio of the ceramic nano line and polymer is (1~15): 100.The present invention realizes in the polymer matrix, it is compound with ceramic nano line with the polymeric matrix of high lithium salt " salt mixes polymer-type " system, new ion transmission path is provided, it promotes lithium ion uniform transmission and inhibits lithium dendrite growth, conductivity is improved, is reached under room temperature (25 DEG C) for 2.13*10‑4S·cm‑1, circulating battery can be carried out with 0.2C at room temperature, discharge capacity is 102mAh/g, capacity retention ratio 84% after 100 circle of circulation.
Description
Technical field
The invention belongs to field of lithium ion battery material more particularly to a kind of salt mix polymer-type composite solid electrolyte and
Preparation method, lithium battery.
Background technique
Lithium ion battery because its high-energy-density, specific power density, it is at low cost the advantages that be widely adopted in each electronic equipment,
And the massive energies such as electric vehicle lay in field.But the organic electrolyte in traditional commerce lithium ion battery exposes in use
Serious safety problem out, such as leakage, burning, explosion, have been unable to meet the demand of people.For this purpose, solid electrolyte mentions
Receiving out with invention in academic and business circles influences extensively and pays close attention to.Organic electrolyte is replaced not only to solve using solid electrolyte
It has determined safety problem, while having also added battery energy density and the advantages such as shape processing is freer, additionally had defeated
The advantages that voltage is high out, working range is wide, good mechanical strength, has widened the application range of lithium ion battery.
Currently, solid electrolyte is broadly divided into two major classes, organic polymer solid electrolyte and inorganic ceramic solid state electrolysis
Matter, wherein the former met bottleneck is that lithium ion conductivity is lower at room temperature, and order of magnitude difficulty is up to 10-4；The latter is then between same electrode
The interface resistance too systemic circulation service life is shorter and preparation cost height, complex process etc., limits the reality of all-solid lithium-ion battery
Border application.
It can be seen that the generally existing preparation process of existing solid electrolyte is complicated, room temperature lithium ion conductivity is low and
Battery cycle life is short, causes using limited problem.
Summary of the invention
The embodiment of the present invention provides a kind of salt and mixes polymer-type composite solid electrolyte, it is intended to solve existing solid state electrolysis
The generally existing preparation process of matter is complicated, room temperature lithium ion conductivity is low and battery cycle life is short, causes using limited skill
Art problem.
The embodiments of the present invention are implemented as follows, and a kind of salt mixes polymer-type composite solid electrolyte, including following components:
Ceramic nano line, polymeric matrix and lithium salts；
The ratio of polymer and lithium salts in the polymeric matrix is (4~11): 1；The ceramic nano line with polymerize
The total mass ratio of object is (1~15): 100.
The embodiment of the invention also provides the preparation methods that a kind of salt mixes polymer-type composite solid electrolyte, comprising:
Polymeric matrix is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；
Lithium salts is weighed according to quantity, and is added in first mixed liquor, is stirred evenly, is obtained the second mixed liquor；
Ceramic nano line is weighed according to quantity, and is added in second mixed liquor, and stirring is equal to ceramic nano line dispersion
After even, third mixed liquor is obtained；
The third mixed liquor is poured into Teflon mould, vacuum drying to get.
The embodiment of the invention also provides a kind of lithium battery, the lithium battery is by anode, cathode and is located at positive and negative
Electrolyte composition between pole, the electrolyte are that above-mentioned salt mixes polymer-type composite solid electrolyte and/or above-mentioned preparation side
The obtained salt of method mixes polymer-type composite solid electrolyte.
Salt provided in an embodiment of the present invention mixes polymer-type composite solid electrolyte, by ceramic nano line, polymeric matrix
And lithium salts composition, on the one hand, it is compound with the progress of ceramic nano line filler by substrate of polymer, overcome inorganic ceramic solid-state
Electrolyte and the big problem of interelectrode interface resistance ensure that solid electrolyte works under room temperature environment or when working and room temperature
With excellent cycle performance；On the other hand, the present invention realizes in the polymer matrix, with high lithium salt " polymer
The polymeric matrix of in salt (salt mixes polymer-type) " system is compound with ceramic nano line, provides new ion transmission road
Diameter promotes lithium ion uniform transmission and inhibits lithium dendrite growth, improves lithium ion conductivity, reach and be under room temperature (25 DEG C)
2.13*10-4S·cm-1, circulating battery can be carried out with 0.2C at room temperature, discharge capacity is 102mAh/g after 100 circle of circulation, is held
Discharge capacity is protected up to 127.1mAh/g, capacity after measuring conservation rate is 84%, also, 0.2C circulation 200 encloses at 40 DEG C
Holdup is 83%.
Detailed description of the invention
Fig. 1 is that (a) provided in an embodiment of the present invention LLZO, (c) LLZAO, (e) LLZTO receive in 700 degree of sintered ceramics
Rice noodles and (b) LLZO, (d) LLZAO, (f) LLZTO are in the SEM morphology characterization figure of 800 degree of sintering thickness ceramic nano lines；
Fig. 2 is XRD curve graph after LLZO, LLZAO provided in an embodiment of the present invention are calcined at 700 DEG C, 800 DEG C；
Fig. 3 is XRD curve graph after LLZTO provided in an embodiment of the present invention is calcined at each temperature；
Fig. 4 is that salt provided in an embodiment of the present invention mixes polymer-type composite solid electrolyte with ceramic nano line content percentage
Than the variation diagram of the conductivity of variation；
Fig. 5 be lithium salt ratio PEO:LiTFSI=11:1 provided in an embodiment of the present invention polymer substrate (a) and
The polymer substrate of lithium salt ratio PEO:LiTFSI=6:1 is the same as compound the surveyed ionic mobility (b) of 10%LLZTO nano wire
And its metal lithium electrode SEM figure (c, d) after Li dendrite loop test is carried out at 0.1mA；
Fig. 6 is the DSC table that salt provided in an embodiment of the present invention mixes polymer-type composite solid electrolyte and polymeric matrix
Sign figure；
Fig. 7 is that salt provided in an embodiment of the present invention mixes polymer-type composite solid electrolyte in flat state and bending state
When AC impedance figure；
Fig. 8 is that salt provided in an embodiment of the present invention mixes polymer-type composite solid electrolyte using the positive lithium of LiFePO4 work
Metal as cathode be assembled into button cell after electricity carried out based on (b) at blue electric battery test system at room temperature (a) and 40 DEG C
Pond charge-discharge test result figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, and does not have to
It is of the invention in limiting.
In embodiments of the present invention, ceramic nano line is lithium lanthanum zirconium oxygen nano wire (LLZO NWs), lithium lanthanum zirconium alumina nanometer
One of line (LLZAO NWs), lithium lanthanum zirconium tantalum oxygen nano wire (LLZTO NWs), above-mentioned lithium lanthanum zirconium oxygen nano wire (LLZO
NWs), lithium lanthanum zirconium alumina nano wire (LLZAO NWs), lithium lanthanum zirconium tantalum oxygen nano wire (LLZTO NWs) are homemade.Its conduct
Nano wire ceramic packing has the function of providing a variety of effective ways for lithium ion transport, increases solid electrolyte ionic conduction
Rate, wherein carbuncle type nano wire filler has the function of inhibiting lithium dendrite growth in metal lithium electrode battery.
Wherein, LLZO NWs's the preparation method comprises the following steps: by lithium nitrate, lanthanum nitrate hexahydrate, zirconium-n-propylate according to
Li7La3Zr2O12The ratio of composition weighs, and being dissolved in n,N-Dimethylformamide (DMF) to analyze pure and glacial acetic acid volume ratio is 5:1
In the mixed solvent, obtain spinning precursor solution after appropriate polyvinylpyrrolidone (PVP) stirring and dissolving is added after dissolution,
In, PVP and DMF mass ratio are 5%~20%.It is placed in syringe and carries out electrostatic spinning, wherein 12~20KV of spinning voltage, needle
Head is collected on aluminium foil with receiver distance about 15cm, gained fiber.It removes to obtain spinning fibre from aluminium foil, be forged in Muffle furnace
Burn to get.
Wherein, LLZAO NWs's the preparation method comprises the following steps: by lithium nitrate, lanthanum nitrate hexahydrate, zirconium-n-propylate, nine nitric hydrates
Aluminium is according to Li6.25La3Zr2Al0.25O12The ratio of composition weighs, preparation of the subsequent preparation process with above-mentioned LLZO nano wire
Method.
Wherein, LLZTO NWs's the preparation method comprises the following steps: by lithium nitrate, lanthanum nitrate hexahydrate, zirconium-n-propylate, ethanol tantalum according to
Li6.75La3Zr1.75Ta0.25O12The ratio of composition weighs, preparation method of the subsequent preparation process with above-mentioned LLZO nano wire.
Meanwhile the present invention shows calcination temperature, calcination time and the change for calcining rate of spinning fibre through many experiments
Change directly affects gained lithium lanthanum zirconium oxygen nano wire (LLZO NWs), lithium lanthanum zirconium alumina nano wire (LLZAO NWs), lithium lanthanum zirconium tantalum oxygen
The pattern and crystal form of nano wire (LLZTO NWs) show as continuous nanowire-type and carbuncle type to obtain SEM pattern
Cubic phase crystal form, the calcination temperature of spinning fibre are preferably 600 DEG C~900 DEG C, and more preferably 700 DEG C~800 DEG C, calcination time
Preferably 1~4h, more preferably 2~3h, heating rate preferably 1 DEG C of min-1~5 DEG C of min-1。
In embodiments of the present invention, polymeric matrix is Pluronic F-127 (PEO), can directly pass through and be commercially available,
Play the role of matrix in the embodiment of the present invention, while having the function of lithium ion conduction.
In embodiments of the present invention, lithium salts is double trifluoromethanesulfonimide lithiums (LiTFSI), can be purchase gained,
Being mixed into PEO in embodiments of the present invention is matrix component part, as the lithium source in solid electrolyte, while also having reduction
It is enriched with anion when PEO crystallinity, high concentration and increases lithium ion transport path, improves the effect of PEO ionic conductivity.
In embodiments of the present invention, the ratio of the polymer in the polymeric matrix and lithium salts is (4~11): 1, specifically
Refer to molar ratio of the monomer with lithium ion in lithium salts of polymer；The total mass ratio of the ceramic nano line and polymer be (1~
15):100。
Salt provided in an embodiment of the present invention mixes polymer-type composite solid electrolyte, by ceramic nano line, polymeric matrix
And lithium salts composition, on the one hand, it is compound with the progress of ceramic nano line filler by substrate of polymer, overcome inorganic ceramic solid-state
Electrolyte and the big problem of interelectrode interface resistance ensure that solid electrolyte works under room temperature environment or when working and room temperature
With excellent cycle performance；On the other hand, the present invention realizes in the polymer matrix, and with high lithium salt, " salt mixes polymerization
The polymeric matrix of object type " system is compound with ceramic nano line, provides new ion transmission path, it is uniform to promote lithium ion
Transmission inhibits lithium dendrite growth, improves lithium ion conductivity, reaches under room temperature (25 DEG C) for 2.13*10-4S·cm-1, can be with
At room temperature 0.2C carry out circulating battery, circulation 100 circle after discharge capacity be 102mAh/g, capacity retention ratio 84%, also,
Discharge capacity is up to 127.1mAh/g, capacity retention ratio 83% after 0.2C circulation 200 encloses at 40 DEG C.
Below by way of specific embodiment to the technical effect that salt of the invention mixes polymer-type composite solid electrolyte do into
The explanation of one step.
Embodiment 1
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the molar ratio of the PEO monomer and lithium ion in LiTFSI is 6:1；The total mass ratio of the LLZTO nano wire and PEO is
1:10.
Wherein, the preparation method of LLZTO nano wire be by lithium nitrate, lanthanum nitrate hexahydrate, zirconium-n-propylate, ethanol tantalum according to
Li6.75La3Zr1.75Ta0.25O12The ratio of composition weighs, and is dissolved in n,N-Dimethylformamide (DMF) and analyzes pure and glacial acetic acid body
Product obtains spinning precursor after appropriate polyvinylpyrrolidone (PVP) stirring and dissolving is added after dissolution than the in the mixed solvent for being 5:1
Solution, wherein PVP is 10% with DMF mass ratio.It is placed in syringe and carries out electrostatic spinning, wherein spinning voltage 16KV, syringe needle
With receiver distance about 15cm, gained fiber is collected on aluminium foil.It removes to obtain spinning fibre from aluminium foil, be forged in Muffle furnace
It burns, calcination temperature is preferably 700 DEG C, calcination time 2h, and heating rate is 1 DEG C of min-1To get.
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, dries 24 hours in 60 DEG C of vacuum drying oven to get compound electric
Solve matter film.
Embodiment 2
Salt mixes polymer-type composite solid electrolyte, including following components: LLZAO nano wire, PEO and LiTFSI；Its
In, the molar ratio of the PEO monomer and lithium ion in LiTFSI is 6:1；The total mass ratio of the LLZAO nano wire and PEO is
1:10.
Wherein, the preparation method of LLZAO nano wire is by lithium nitrate, lanthanum nitrate hexahydrate, zirconium-n-propylate, nine nitric hydrates
Aluminium is according to Li6.25La3Zr2Al0.25O12The ratio of composition weighs, and is dissolved in n,N-Dimethylformamide (DMF) and analyzes pure and ice second
Sour volume ratio is the in the mixed solvent of 5:1, obtains spinning after appropriate polyvinylpyrrolidone (PVP) stirring and dissolving is added after dissolution
Precursor solution, wherein PVP is 10% with DMF mass ratio.It is placed in syringe and carries out electrostatic spinning, wherein spinning voltage 16KV,
Syringe needle and receiver distance about 15cm, gained fiber are collected on aluminium foil.It removes to obtain spinning fibre from aluminium foil, in Muffle furnace
Calcining, calcination temperature is preferably 800 DEG C, calcination time 1h, and heating rate is 1 DEG C of min-1To get.
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZAO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZAO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, dries 24 hours in 60 DEG C of vacuum drying oven to get compound electric
Solve matter film.
Embodiment 3
Salt mixes polymer-type composite solid electrolyte, including following components: LLZO nano wire, PEO and LiTFSI；Its
In, the molar ratio of the PEO monomer and lithium ion in LiTFSI is 6:1；The total mass ratio of the LLZO nano wire and PEO are 1:
10。
Wherein, the preparation method of LLZO nano wire be by lithium nitrate, lanthanum nitrate hexahydrate, zirconium-n-propylate according to
Li7La3Zr2O12The ratio of composition weighs, and being dissolved in n,N-Dimethylformamide (DMF) to analyze pure and glacial acetic acid volume ratio is 5:1
In the mixed solvent, obtain spinning precursor solution after appropriate polyvinylpyrrolidone (PVP) stirring and dissolving is added after dissolution,
In, PVP and DMF mass ratio are 10%.It is placed in syringe and carries out electrostatic spinning, wherein spinning voltage 16KV, syringe needle and reception
Device distance about 15cm, gained fiber are collected on aluminium foil.It removes to obtain spinning fibre from aluminium foil, be calcined in Muffle furnace, calcined
Temperature is preferably 800 DEG C, calcination time 2h, and heating rate is 1 DEG C of min-1To get.
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZO nano wire is weighed according to quantity, and is added in second mixed liquor,
It is stirred at room temperature 24 hours, after LLZO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；By institute
Third mixed liquor is stated to pour into Teflon mould, in 60 DEG C of vacuum drying oven dry 12 hours to get.
1-3 of the embodiment of the present invention is to change ceramic nano line, remaining content and the constant experimental group of process conditions pass through friendship
Flow impedance method, which is tested, above-mentioned mixes the lithium ion of polymer-type composite solid electrolyte at room temperature according to the resulting salt of embodiment 1-3
Conductivity, the results are shown in Table 1:
Salt obtained by 1 embodiment 1-3 of table mixes the lithium ion conductivity of polymer-type composite solid electrolyte at room temperature
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Lithium ion conductivity (Scm-1) | 2.13*10-4 | 1.85*10-4 | 1.73*10-4 |
To sum up, as known from Table 1, salt obtained by embodiment 1-3 mix the lithium of polymer-type composite solid electrolyte at room temperature from
Electron conductivity reaches 10-4S·cm-1, solve the prior art at room temperature lithium ion conductivity order of magnitude difficulty up to 10-4, lithium from
The low problem of electron conductivity, reason are in the embodiment of the present invention that filler enhances the conduction of lithium ion using nanowire-type pattern
Mechanism improves lithium ion conductivity；Wherein, polymer-type composite solid is mixed using 1 gained salt of the embodiment of LLZTO nano wire
The lithium ion conductivity of electrolyte at room temperature is apparently higher than the embodiment 2-3 using LLZO and LLZAO nano wire, according to right
The pattern and XRD Crystalline form analysis for forming ceramic nano line under different temperatures calcining are it is found that lithium ion conductivity is directly made pottery
The influence of the pattern and crystal form of porcelain nano wire.
Specifically, LLZO, LLZAO, LLZTO as shown in Figure 1 in 700 DEG C of sintered ceramic nano lines and LLZO,
LLZAO, LLZTO in 800 DEG C of sintered ceramic nano lines SEM morphology characterization it is found that the ceramics calcined at 700 DEG C are received
Rice noodles diameter is about 200nm~300nm, and gained nano wire keeps continuous；Further, non-impurity-doped LLZO and Al as shown in Figure 2
The XRD characterization result that the LLZO ceramic nano line of doping is sintered at different temperatures is it is found that the two is sintered gained crystalline substance at 700 DEG C
Type is not pure, and 800 DEG C of sintering can obtain required carbuncle type cubic phase but still have a small amount of impurity, to subsequent composite electrolyte
Lithium ion conductivity has adverse effect；And the LLZTO ceramic nano line XRD characterization of Ta doping can obtain as shown in Figure 3,700
DEG C, be sintered at 800 DEG C and can obtain carbuncle type cubic phase, accordingly, it is determined that optimal calcination temperature and calcination time are 700 DEG C of burnings
Tie 3h.
Further, on the basis of embodiment 1,700 DEG C of resulting LLZTO nano wires of sintering 3h are selected as salt and mix polymerization
Ceramic nano line in object type composite solid electrolyte, change each component content, remaining component and processing step are constant, carry out with
Lower embodiment 4-8.
Embodiment 4
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the molar ratio of the PEO monomer and lithium ion in LiTFSI is 4:1；The mass ratio of the LLZTO nano wire and PEO are 1:
100。
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, in 70 DEG C of vacuum drying oven dry 12 hours to get.
Embodiment 5
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the molar ratio of the PEO monomer and lithium ion in LiTFSI is 8:1；The mass ratio of the LLZTO nano wire and PEO are 1:
10。
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, in 60 DEG C of vacuum drying oven dry 24 hours to get.
Embodiment 6
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the molar ratio of the PEO monomer and lithium ion in LiTFSI is 9:1；The mass ratio of the LLZTO nano wire and PEO are 1:
20。
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, in 65 DEG C of vacuum drying oven dry 16 hours to get.
Embodiment 7
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the molar ratio of the PEO monomer and lithium ion in LiTFSI is 11:1；The mass ratio of the LLZTO nano wire and PEO are 3:
20。
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, in 70 DEG C of vacuum drying oven dry 18 hours to get.
4-7 of the embodiment of the present invention is that component and process conditions are constant, changes the experimental group of constituent content, passes through AC impedance
Method, which is tested, above-mentioned mixes the lithium ion conductance of polymer-type composite solid electrolyte at room temperature according to the resulting salt of embodiment 4-7
Rate, the results are shown in Table 2:
Salt obtained by 2 embodiment 4-7 of table mixes the lithium ion conductivity of polymer-type composite solid electrolyte at room temperature
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Lithium ion conductivity (Scm-1) | 2.03*10-4 | 1.23*10-4 | 1.21*10-4 | 1.17*10-4 |
To sum up, as known from Table 2, salt obtained by embodiment 4-7 mix the lithium of polymer-type composite solid electrolyte at room temperature from
Electron conductivity has equally reached 10-4S·cm-1, further demonstrate filler in the embodiment of the present invention and increased using nanowire-type pattern
The strong transmission mechanism of lithium ion, improves lithium ion conductivity, it is notable that embodiment 1 is used with embodiment 4-7
Lithium salt be all different, wherein use the molar ratio of PEO and LiTFSI aobvious for the lithium ion conductivity of the embodiment 1 of 6:1
The lithium ion conductivity of polymer-type composite solid electrolyte is so mixed higher than salt obtained by embodiment 4-7.
Further, the molar ratio for keeping PEO monomer and lithium ion in LiTFSI on the basis of embodiment 1 is that 6:1 is constant,
Change the mass ratio (1%, 5%, 10% and 15%) of LLZTO nano wire and PEO, remaining preparation process condition is constant, carries out
Following example 8-11.
Embodiment 8
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the mass ratio of the LLZTO nano wire and PEO are 1:100 (1%)；Mole of the PEO monomer and lithium ion in LiTFSI
Than for 6:1.
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, in 60 DEG C of vacuum drying oven dry 24 hours to get.
Embodiment 9
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the mass ratio of the LLZTO nano wire and PEO are 1:20 (5%)；Mole of the PEO monomer and lithium ion in LiTFSI
Than for 6:1.
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, in 60 DEG C of vacuum drying oven dry 24 hours to get.
Embodiment 10
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the mass ratio of the LLZTO nano wire and PEO are 1:10 (10%)；Mole of the PEO monomer and lithium ion in LiTFSI
Than for 6:1.
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, in 60 DEG C of vacuum drying oven dry 24 hours to get.
Embodiment 11
Salt mixes polymer-type composite solid electrolyte, including following components: LLZTO nano wire, PEO and LiTFSI；Its
In, the mass ratio of the LLZTO nano wire and PEO are 3:20 (15%)；Mole of the PEO monomer and lithium ion in LiTFSI
Than for 6:1.
PEO is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；LiTFSI is weighed according to quantity, and described in addition
It in first mixed liquor, stirs evenly, obtains the second mixed liquor；LLZTO nano wire is weighed according to quantity, and second mixed liquor is added
In, it is stirred at room temperature 24 hours, after LLZTO nano wire is fully dispersed in the second mixed liquor, obtains third mixed liquor；
The third mixed liquor is poured into Teflon mould, in 60 DEG C of vacuum drying oven dry 24 hours to get.
1 blank control group of comparative example
It weighs PEO to be dissolved into acetonitrile solvent, LiTFSI, EO:Li is then added+Ratio be 6:1, be added lithium salts after,
It is stirred at room temperature 2 hours, is then poured into polytetrafluoroethylene PTFE mold, it is 24 hours dry in 60 DEG C of vacuum drying oven, i.e.,
It obtains polymer electrolyte film (SPE).
Comparative example 2
On the basis of embodiment 10, LLZTO nano wire (LLZTO NWs) is replaced with into LLZTO nano particle (LLZTO
NPs), remaining component and preparation process condition are constant.
Test case 1
Dielectric film conductivity is surveyed by AC impedence method, salt obtained by 8-11 of the embodiment of the present invention is mixed into polymer-type respectively
Composite solid electrolyte (SPE-1%LLZTO NWs, SPE-5%LLZTO NWs, SPE-10%LLZTO NWs, SPE-15%
LLZTO NWs) and comparative example 1-2 gained electrolyte (PEO6(LiTFSI) and SPE-10%LLZTO NPs) be clipped in two steel
After being assembled between piece using 2016 type battery cases, ac impedance spectroscopy is surveyed in the frequency range of 3MHz~1Hz, passes through formula (1) and calculates
The composite electrolyte lithium ion conductivity σ of different nano wire percentages must be contained as shown in figure 4, wherein preferably 10% doping ceramics
Nano wire lithium ion conductivity is optimal, at room temperature up to 2.13 × 10-4S·cm-1；In addition, the SPE-10% of doped nanoparticle
Well below the lithium ion conductivity for the nano wire for adulterating same mass ratio, reason is the lithium ion conductivity of LLZTO NPs:
Solid polymer matrix itself lithium ion conductivity is lower, is adulterated by active particles, though solid polymer electrolyte is substantially improved
The lithium ion conductivity of matter, but nano particle cannot effectively provide ion transmission path, and ionic conduction is weaker at room temperature.
σ is lithium ion conductivity, RbFor composite electrolyte membrane bulk resistance, S is dielectric film with steel disc contact area, l
For Electrolyte film thickness.
It is worth noting that, 8-11 of the embodiment of the present invention accounts for entire gather in PEO matrix, to add the levels of lithium salts
50% or more of polymer matrix, to PEO, LLZTO nanometers of each component in 1 gained solid electrolyte of embodiment 8-11 and comparative example
Mass percent shared by line (LLZTO NWs) and LiTFSI is calculated, and the results are shown in Table shown in 3.
Table 3
Test case 2
By permanent potential test and ac impedance measurement to the pure polymer substrates of PEO:LiTFSI=11:1 in embodiment 5
It mixes in polymer-type composite solid electrolyte and embodiment 11 with salt of the 10% ceramic nano line after compound using PEO:
The polymer substrate of LiTFSI=6:1 mixes the lithium of polymer-type composite solid electrolyte with salt of the 10% ceramic nano line after compound
Transference number of ions measures, acquired results are as follows: lithium salt is than the pure polymer substrates ion for PEO:LiTFSI=11:1
Transport number is 0.25, and lithium ion transference number is promoted to 0.48 after adding 10% ceramic nano line；Using PEO:LiTFSI=6:1
Polymer substrate mix the lithium ionic mobility of polymer-type composite solid electrolyte with salt of the 10% ceramic nano line after compound
Further it is promoted to 0.57.And under 0.1uA electric current after progress Li dendrite long circulating test, SEM table is carried out to metal lithium electrode
Sign generates more Li dendrite by Fig. 5 (c) is visible under low concentration lithium salts, by Fig. 5 (d) using high salt concentration polymeric substrates
Salt, which mixes polymer-type composite solid electrolyte, has the function of dendrite inhibition growth.
Wherein, lithium ion transference number tLi+Measurement method is to use 2016 type battery cases after composite electrolyte both sides press from both sides lithium piece
Assembling carries out permanent potential measurement under constant voltage △ V=0.01mV, carries out ac impedance measurement respectively afterwards before measuring, rear to use
Formula (2) calculates gained:
tLi +For transference number of ions, i0For initial current, isFor steady-state current, R0 flimFor initial interface impedance, Rs flimIt is steady
State interface impedance.
Test case 3
To SPE (the i.e. EO:Li of the salinity of pure PEO and 50% or more addition+=6:1) carry out DSC test, gained knot
Fruit is crystalline state when room temperature as shown in fig. 6, pure PEO melting peak occurs in about 60 degree, and 50% or more salinity is added
SPE (i.e. EO:Li+=6:1) polymeric matrix do not have a melting peak, and it is unformed that glass transition temperature Tg is about -55 DEG C at room temperature
State decreases after composite nano-line with the increase glass transition temperature of nano wire but changes less, it was demonstrated that the addition pair of nano wire
The crystal structure of polymeric matrix also has an impact, but influences less, and same glass transition temperature is at -55 DEG C hereinafter, when room temperature is compound
Electrolyte is unformed shape, is conducive to the conduction of PEO itself lithium ion, while having to the interelectrode contact of composite electrolyte is improved
Great role.
Test case 4
Embodiment 10 and 2 gained salt of comparative example are mixed into polymer-type composite solid electrolyte and carry out flexible test, as a result
No matter as shown in fig. 7, in the coplanar composite nano-line of composite electrolyte and nano particle polymerizable compound within object matrix of bending status
Afterwards, bulk resistance has no significant change.
Test case 5
(SPE-10%LLZTO NWs) the obtained solid electrolyte of embodiment 10 is made positive lithium metal using LiFePO4 to make
Cathode is assembled into after button cell and carries out battery charging and discharging test based on blue electric battery test system, as a result as shown in figure 8, from figure
It is found that 0.2C carries out circulating battery at room temperature in 8 (a), discharge capacity is 102mAh/g, capacity retention ratio after 100 circle of circulation
Be 84%, also, from Fig. 8 (b) it is found that after 0.2C circulation 200 encloses at 40 DEG C discharge capacity up to 127.1mAh/g,
Capacity retention ratio is 83%.
To sum up, salt provided in an embodiment of the present invention mixes polymer-type composite solid electrolyte, by ceramic nano line, polymer
Matrix and lithium salts composition, it is compound with the progress of ceramic nano line filler by substrate of polymer, overcome inorganic ceramic solid-state electricity
Matter and the big problem of interelectrode interface resistance are solved, ensure that solid electrolyte works or tool when working and room temperature under room temperature environment
There is excellent cycle performance, circulating battery can be carried out with 0.2C at room temperature, discharge capacity is 102mAh/g after 100 circle of circulation,
Discharge capacity is up to 127.1mAh/g, capacity after capacity retention ratio is 84%, also, 0.2C circulation 200 encloses at 40 DEG C
Conservation rate is 83%.
It is worth noting that, the present invention realizes in PEO matrix, with high lithium salt " polymer in salt " (salt
Mix polymer) polymeric matrix of system is compound with ceramic nano line, new ion transmission path is provided, lithium ion is in addition to logical
Cross ceramic self transmission, outside the transmission in polymer between transmission, ceramics and polymer interface, increase lithium ion by lithium
The transmission mechanism transmitted between the anion of salt promotes lithium ion uniform transmission and inhibits lithium dendrite growth, improves lithium ion conductance
Rate reaches under room temperature (25 DEG C) for 2.13*10-4S·cm-1, while high concentration lithium salts reduces the crystallinity of polymer, makes
Obtain polymer is also amorphous state at room temperature.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of salt mixes polymer-type composite solid electrolyte, which is characterized in that including following components: ceramic nano line, polymerization
Object matrix and lithium salts；
The ratio of polymer and lithium salts in the polymeric matrix is (4~11): 1；The ceramic nano line and polymer
Total mass ratio is (1~15): 100.
2. salt as described in claim 1 mixes polymer-type composite solid electrolyte, which is characterized in that in the polymeric matrix
Polymer and lithium salts ratio be 6:1.
3. salt as described in claim 1 mixes polymer-type composite solid electrolyte, which is characterized in that the polymeric matrix is
Pluronic F-127.
4. salt as described in claim 1 mixes polymer-type composite solid electrolyte, which is characterized in that the lithium salts is double trifluoros
Sulfonyl methane imine lithium.
5. salt as described in claim 1 mixes polymer-type composite solid electrolyte, which is characterized in that the ceramic nano line is
One of lithium lanthanum zirconium oxygen nano wire, lithium lanthanum zirconium alumina nano wire, lithium lanthanum zirconium tantalum oxygen nano wire.
6. salt as claimed in claim 5 mixes polymer-type composite solid electrolyte, which is characterized in that the lithium lanthanum zirconium tantalum oxygen is received
Rice noodles the preparation method comprises the following steps:
By lithium nitrate, lanthanum nitrate hexahydrate, zirconium-n-propylate, ethanol tantalum according to Li6.75La3Zr1.75Ta0.25O12The molar ratio of composition
Example weighs, spare；
The lithium nitrate, lanthanum nitrate hexahydrate, zirconium-n-propylate, ethanol tantalum are dissolved in the mixed of N,N-dimethylformamide and glacial acetic acid
In bonding solvent, mixed liquor is obtained；
Polyvinylpyrrolidone is added in the mixed liquor, and stirs until dissolution, obtains spinning precursor solution；
The spinning precursor solution is placed in syringe and carries out electrostatic spinning, obtains fibre spinning；
By the fibre spinning be placed in temperature be 600 DEG C~900 DEG C at, calcine 1~4h to get.
7. salt as claimed in claim 6 mixes polymer-type composite solid electrolyte, which is characterized in that the fibre spinning is forged
Burning temperature is 700 DEG C~800 DEG C；Calcination time is 2~3h.
8. the preparation that a kind of salt as described in any one of claim 1~7 claim mixes polymer-type composite solid electrolyte
Method characterized by comprising
Polymeric matrix is weighed according to quantity, and is dissolved into acetonitrile solvent, and the first mixed liquor is obtained；
Lithium salts is weighed according to quantity, and is added in first mixed liquor, is stirred evenly, is obtained the second mixed liquor；
Ceramic nano line is weighed according to quantity, and is added in second mixed liquor, after stirring is uniformly dispersed to the ceramic nano line,
Obtain third mixed liquor；
The third mixed liquor is poured into Teflon mould, vacuum drying to get.
9. the preparation method that salt as claimed in claim 8 mixes polymer-type composite solid electrolyte, which is characterized in that described true
Empty drying temperature is 60 DEG C~80 DEG C；Vacuum drying time is 12~24 hours.
10. a kind of lithium battery, the lithium battery is made of anode, cathode and the electrolyte between anode and cathode,
Be characterized in that: the electrolyte is that salt described in any one of claim 1~7 claim mixes the electrolysis of polymer-type composite solid
Any one of matter and/or the claim 8/9 obtained salt of preparation method mix polymer-type composite solid electrolyte.
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