CN109921024A - A kind of flexible solid-state lithium ion conductor applied to battery and preparation method thereof - Google Patents
A kind of flexible solid-state lithium ion conductor applied to battery and preparation method thereof Download PDFInfo
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- CN109921024A CN109921024A CN201910185272.6A CN201910185272A CN109921024A CN 109921024 A CN109921024 A CN 109921024A CN 201910185272 A CN201910185272 A CN 201910185272A CN 109921024 A CN109921024 A CN 109921024A
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- lithium ion
- lithium
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 112
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000010416 ion conductor Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 41
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- -1 LiCF 3 SO 3 Inorganic materials 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000001979 organolithium group Chemical group 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 238000000861 blow drying Methods 0.000 claims 1
- 125000000879 imine group Chemical group 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 43
- 239000000463 material Substances 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 125000000707 boryl group Chemical group B* 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 208000032953 Device battery issue Diseases 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- IPLJXALXGKSNPT-UHFFFAOYSA-N benzenesulfonic acid;lithium Chemical compound [Li].OS(=O)(=O)C1=CC=CC=C1 IPLJXALXGKSNPT-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920005574 polyvinylidene vinyl fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013164 LiN(FSO2)2 Inorganic materials 0.000 description 1
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007582 slurry-cast process Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The present invention provides a kind of flexible solid lithium ion conductor and preparation method thereof, belongs to energy stores and transition material technical field.The flexible lithium ion conductor includes at least two kinds of components containing lithium ion, wherein: a component is inorganic or organic lithium salts, another component is polymer, at least one on main chain with ether-oxygen bond, carbon nitrogen singly-bound, C=O bond or silicon oxygen bond, and contain the lithium ion being coordinated with ionic bond.Solid lithium ion conductors of the invention are the flexible body with plasticity, conductivity at room temperature > 10‑4S/cm, lithium ion transference number > 0.4.Flexible solid lithium ion conductor of the invention is applied in the solid state battery including lithium ion battery, lithium metal battery, lithium-sulfur cell and lithium-air battery, due to high-lithium ion conductivity, high tensile strength and certain plastic deformation ability, it can be used as binder and introduce electrode, or it is used as solid electrolyte simultaneously, excellent interface stability and cycle life is presented.
Description
Technical field
The invention belongs to energy stores and transition material technical field, in particular to a kind of solid lithium ion conductors flexible
And preparation method, and its application as binder and electrolyte in the battery.
Background technique
Lithium ion conductor be can conducting lithium ions and the substance of electronic isolation, in lithium ion battery, lithium metal battery, lithium sulphur
The important medium of lithium ion conduction in battery and lithium-air battery is the critical material for ensureing normal battery operation.Currently, universal
The lithium ion conductor of use is liquid, plays in liquid system that lithium ion mobility rate is fast, conductivity is high by (>=10-3S/cm)
Advantage, and liquid lithium ion conductor have mobility, can impregnating porous electrode, thus in the battery building lithium ion pass
The continuous passage led, therefore the lithium ion conductor of liquid applies maturation in energy stores and conversion equipment.But liquid lithium from
Sub- conductor application limit battery energy density further increase and the flexible design of cell shapes, especially semi-open
Volatilization with liquid lithium ion conductor in the lithium-air battery of Full-open, which is dried up, directly results in battery failure.Moreover, even more serious
Be thus bring security risk, such as volatilization burning, leakage cause explosion etc. accidents.Solid lithium ion conductors can not only gram
The shortcomings that taking liquid system, and the lower solid lithium ion conductors of density with plasticity can prepare flexibly and fracture toughness is excellent
It is different, it ensure that the diversification of battery design, substantially reduce manufacturing cost, improve the energy density of lithium ion battery.Therefore, flexible
Solid lithium ion conductors are considered as a kind of important material for being most hopeful to break through the exploitation of more secure and reliable higher energy densitybattery
Material.
Currently, solid lithium ion conductors are often rigid, lack plastic deformation ability.In the prior art, it is common that
Certain polymer is mixed into the solid lithium ion conductors such as organic lithium salt and inorganic lithium salt to increase flexibility, but is increasing polymer
While content, it cannot be considered in terms of the performances such as the lithium ion conductivity, lithium ion transference number and plastic deformation ability of system.These
The dissociation in the polymer of performance and solid lithium ion conductors and migration are directly related, and by solid lithium ion conductors and polymer
Type and interaction between the two determined.In addition to organic lithium salt and inorganic lithium salt, lithium single ion conductor is also
Solid lithium ion conductors, and some single ion conductors are polymer, but the conductivity of single ion conductor polymer is general at present
All over lower, conductivity at room temperature is 10-5~10-8Within the scope of S/cm.[the Jounal of such as Geiculescu
Electrochemical Society, 2004,151 (9): A1363-1368] it synthesizes containing oroalkane sulfonyl imines of enjoying a double blessing
The lithium single ion conductor of anion structure unit, even if room-temperature conductivity is blended with PEO still down to 10-7S/cm；Bouchet and
Armand etc. [Natrue Material, 2013,12:452] has synthesized polymer lithium single ion conductor P (STFSILi)-b-
PEO-b-P (STFSILi), conductivity is about 1.3 × 10 at 60 DEG C-5S/cm.The base proposed in patent ZL201310302904.5
Reach 10 in the conductivity at room temperature of polyvinyl formal or all solid state polyelectrolyte membrane of its homologue-6S/cm.Cause
This, need at present development be provided simultaneously with the lithium of high-lithium ion conductivity, high-lithium ion transport number, high mechanical strength and high-ductility from
Sub- conductor material is high-energy density and high security lithium ion battery, lithium metal battery, lithium-sulfur cell and lithium-air battery
Design and development provide critical material.
Summary of the invention
The object of the present invention is to provide a kind of flexible solid lithium ion conductors, are provided simultaneously with high-lithium ion conductivity, height
Lithium ion transference number, high mechanical strength and high-ductility, and the application as binders for electrodes and electrolyte in the battery.
A kind of flexible solid lithium ion conductor provided by the invention includes at least following two containing the component of lithium ion:
Lithium salts and polymer.The lithium salts is organic lithium salt, has the combination energy lower than 515 kJ/mol.The polymer has
General formula structure (1):
(1)
R in its general structure (1)1And R2Independently of each other, R1At least one containing following group: ether-oxygen bond (- C-O-C-),
Carbon nitrogen singly-bound (- C-N-), C=O bond (- C=O-) or silicon oxygen bond (- Si-O-)；Lithium ion is bonded on R2 by ionic bond, and
1 x:y≤4 <.Wherein, organic lithium salt contains boryl, sulfonic group, phosphate or imido grpup, and relative molecular mass is greater than 143 and is less than
470.And particularly preferably from least one LiODFB, LiBOB, LiCF of following substance3SO3、LiN(SO2CF3)2、LiN
(SO2C2F5)2、Li(C2F5)3PF3、LiN(FSO2)2、ddCTP-Li3。
A kind of flexible solid lithium ion conductor provided by the invention, preparation method includes the following steps: polymer is filled
It point is dissolved into organic solvent, adds organic lithium salt and reach abundant dissolution, form solution, wherein polymer and organic lithium salt
Ratio reaches: the molar ratio of the lithium ion content of the content and organic lithium salt of functional group R1 is 5:1- in Polymer Formulation structure 1
50:1；Then solution is heated to 40-120 DEG C, stirs 2-36h, obtains slurry；Finally, slurry is placed at 40 DEG C -100 DEG C,
Forced air drying or vacuum drying；Or uniformly coat slurry or tape casting, it is finally placed it at 40 DEG C -100 DEG C again, drum
Air-dry dry or vacuum drying.
A kind of flexible solid lithium ion conductor provided by the invention is as disposable lithium-battery, secondary lithium battery or secondary
The binder of the positive or negative pole of lithium metal battery；Perhaps solid state battery is used as the electrolyte of solid state battery or simultaneously
Positive or negative pole binder and electrolyte.
The invention has the following advantages that
Polymer in flexible solid lithium ion conductor of the present invention contains the lithium ion being bonded with ionic bond, simultaneously
At least one containing ether-oxygen bond (- C-O-C-), carbon nitrogen singly-bound (- C-N-), C=O bond (- C=O-) or silicon oxygen bond (- Si-O-)
Kind, there is strong dissolution lithium salts and the coordination ability with lithium ion, for example, since oxygen element is stronger in-C-O-C- ether-oxygen bond
Electronegativity, so that carbon-oxygen chemical key is shown as polar covalent bond, shared electron opposite direction oxygen atom deviates, so that the oxygen of ether-oxygen bond
There is stronger electron donation, while oxygen atom has two pairs of lone pair electrons on atom, so that ether oxygen base has lithium ion
Strong coordination ability.In turn, the high-efficiency dissolution of the component-lithium salts for containing lithium ion for another in the polymer creates condition.
R in the polymers compositions of solid lithium ion conductors flexible of the present invention1And R2Independently of each other, R1With R2Mole
Than x:y in 1 range of < x:y≤4, the locomitivity of polymer molecule has been ensured.If R1With R2Ratio excessively high go beyond the scope
When, solvation simultaneously assists Li+The structural unit of transmission is too low, causes ionic conductivity relatively low；If R1With R2Ratio it is too low when,
Cause lithium ion transference number relatively low.With general structure (1) and reach the polymer of corresponding requirements, guarantee plurality of group with
One lithium ion generates association-dissociation, continuous lithium ion transport channel is formed, to promote the migration of lithium ion.
Another component is organic lithium salt in flexible solid lithium ion conductor of the present invention, has and is lower than 515 kJ/
The combination energy of mol has ensured the dissolution and dissociation of lithium salts in the polymer.Moreover, the R in polymer1Polar groups are deposited
Chemical environment is created in the dissolution of more lithium salts in the polymer.Flexible solid lithium ion conductor of the present invention is from system
Component constitutes and two angles of interaction, solves the concentration of the i.e. transportable lithium ion of carrier in current polymeric system
The technical problem being difficult to improve.And lithium salts is dissolved in the polymers compositions of system, free anion reduces polymerization
The intermolecular active force with intramolecular of object, improves the locomitivity of segment, has ensured the transmittability of carrier.In summary special
Sign, flexible solid lithium ion conductor of the present invention, which has reached, is provided simultaneously with conductivity at room temperature higher than 10-4S/cm, lithium
Transference number of ions is greater than the performance advantage of 0.4, the tensile strength higher than 15 MPa and the plastic deformation greater than 30%.Solves mesh
Preceding lithium ion conductor cannot be considered in terms of the technical problem of lithium ion conductivity, lithium ion transference number and plastic deformation ability.
Flexible solid lithium ion conductor of the present invention is as the binder of anode or cathode, the electricity of solid state battery
Xie Zhi, or the binder and electrolyte as the positive or negative pole of solid state battery simultaneously, significantly improve the energy density of battery
And cycle life.
Detailed description of the invention
Fig. 1 is the SEM image of lithium ion conductor prepared by embodiment 1.
Fig. 2 is the SEM image of lithium ion conductor prepared by comparative example 1.
Fig. 3 is the test result that the conductivity of lithium ion conductor prepared by embodiment 2 varies with temperature.
Fig. 4 is electric current-polarization time curve of lithium ion conductor prepared by embodiment 2.
Fig. 5 is the test result that the conductivity of lithium ion conductor prepared by comparative example 2 varies with temperature.
Fig. 6 is electric current-polarization time curve of lithium ion conductor prepared by comparative example 2.
Fig. 7 is tensile strength-strain curve of lithium ion conductor prepared by embodiment 3.
Fig. 8 be embodiment 4 prepare lithium ion conductor as positive electrode binder be assembled into battery after loop test curve.
Specific embodiment:
It will be described in more detail below by embodiment, but protection scope of the present invention is not limited to embodiment.
Embodiment 1
(1) for polymer using single Lithium bis (oxalate) borate grafting polyvinyl alcohol formal, structural formula is as follows, wherein lower x:y=4.
It weighs the above polymer 0.4305g to be dissolved in 2.583g dimethyl sulfoxide, is sufficiently stirred and makes it completely dissolved.
(2) the organic lithium salt LiODFB(relative molecular mass 144 that 0.031g contains boryl is continuously added), corresponding general formula knot
Structure R1(1,3- dioxane) and organic lithium salt LiODFB lithium ion molar ratio be 15:1, formed solution.
(3) solution is then heated to 70 DEG C of stirrings for 24 hours, obtains slurry, then slurry is uniformly coated on glass plate,
It is dried in vacuo at 50 DEG C for 24 hours, obtains flexible solid lithium ion conductor.
Flexible solid lithium ion conductor microstructure obtained by embodiment 1 is as shown in Figure 1, the lithium ion conductor as seen from the figure
For surface compact and uniform film.Lithium ion transference number is 0.67, and room-temperature conductivity is 4.77 × 10-4S/cm, as solid
State electrolyte matches assembling half-cell with iron phosphate lithium electrode, and capacity retention ratio is after recycling 100 times at 55 DEG C, 0.3C
83.9%。
Comparative example 1
(1) for polymer using single Lithium bis (oxalate) borate grafting polyvinyl alcohol, structural formula is as follows, wherein lower x:y=0.Weigh with
Upper polymer 0.4305g is dissolved in 2.583g dimethyl sulfoxide, is sufficiently stirred and is made it completely dissolved.
(2) the organic lithium salt LiODFB that 0.031g contains boryl is continuously added, solution is formed.
(3) solution is then heated to 50 DEG C of stirrings for 24 hours, obtains slurry, then slurry is uniformly coated on glass plate,
It is dried in vacuo at 50 DEG C for 24 hours, obtains solid lithium ion conductors sample.
Lithium ion conductor microstructure obtained by comparative example 1 is as shown in Fig. 2, the lithium ion conductor film surface as seen from the figure
Lithium salt particles precipitation phenomenon is serious, illustrates that dissolution of the organic lithium salt LiODFB in polymeric system is incomplete, remaining is organic
Lithium salts is segregated in lithium ion conductor.And there are macropore appearance, organic lithium salt on lithium ion conductor film obtained by comparative example 1
The dissolution and segregation of LiODFB produces the flexibility and Film Morphology of polymer and seriously affects.Unlike the first embodiment, right
Polymer in ratio 1 does not have general formula structure (1), without containing the R in general structure (1)1Unit, therefore lead to polymer energy
It enough dissolves and the ability for dissociating lithium salts is limited, this is current polymeric system common problem.The resulting lithium of comparative example 1 from
The conductivity at room temperature and lithium ion transference number of sub- conductor are well below the flexible lithium ion conductor that embodiment 1 provides.It is right
Lithium ion conductor prepared by ratio 1 matches assembling half-cell as solid electrolyte with LiFePO4, recycles at 55 DEG C, 0.3C
Battery failure after 7 times, cycle performance can not show a candle to the flexible lithium ion conductor that embodiment 1 is prepared by the method for the invention.
Embodiment 2
(1) polymer uses benzene sulfonic acid lithium grafted polyvinylidene vinyl fluoride, and structural formula is as follows, wherein x:y=1.2:1.It takes above
Polymer 0.7231g is dissolved in 3.32g acetonitrile, is sufficiently stirred and is made it completely dissolved.
(2) the organic lithium salt LiBETI(relative molecular mass 387 that 0.054g has sulfimide moiety is continuously added),
Corresponding general formula structure R1(- CH2-CF2) it with the molar ratio of organic lithium salt LiBETI lithium ion is 50:1, form solution.
(3) solution is then heated to 40 DEG C of stirring 30h, obtains slurry.Finally, slurry is dried in vacuo at 60 DEG C
36h obtains flexible solid lithium ion conductor.
The ac impedance measurement result of flexible solid lithium ion conductor obtained by embodiment 2 is as shown in figure 3, at 25 DEG C of room temperature
Under, the room-temperature conductivity of the lithium ion conductor is 6.84 × 10-4S/cm.If electric current-polarization time curve of Fig. 4 can obtain, implement
The lithium ion transference number of flexible solid lithium ion conductor obtained by example 2 is 0.71.
Comparative example 2
(1) polymer uses benzene sulfonic acid lithium grafted polyvinylidene vinyl fluoride, and structural formula and the polymer phase of embodiment 2 are same, wherein x:y
= 1.2:1.It weighs the above polymer 0.7231g to be dissolved in 3.32g acetonitrile, is sufficiently stirred and makes it completely dissolved.
(2) 0.023g organic lithium salt LiBF is continuously added4(relative molecular mass 93), corresponding general formula structure R1(- CH2-
CF2) and organic lithium salt LiBF4Lithium ion molar ratio be 50:1, formed solution.
(3) solution is then heated to 40 DEG C of stirring 30h, obtains slurry.Finally, slurry is dried in vacuo at 60 DEG C
36h obtains solid lithium ion conductors.
The room-temperature conductivity for the solid lithium ion conductors that comparative example 2 obtains is 1.61 × 10-5S/cm(Fig. 5), lithium ion
Transport number is 0.29(such as Fig. 6).2 difference from Example 2 of comparative example is: organic lithium salt is LiBF in comparative example 24(phase
To molecular mass 93) do not contain the functional groups such as boryl, boryl, sulfonic group, phosphate or imido grpup, the organolithium in embodiment 2
Salt is the organic lithium salt LiBETI(relative molecular mass 387 with sulfimide moiety).
Embodiment 3
(1) polymer is grafted poly- ethylene carbonate using perfluoroalkyl carboxyl lithium, and structural formula is as follows, wherein x:y=2.4:
1.It weighs the above polymer 0.6471g to be dissolved in 2.983g tetrahydrofuran, is sufficiently stirred and makes it completely dissolved.
(2) the organic lithium salt ddCTP-Li that 0.151g contains phosphate group is continuously added3(relative molecular mass 469), it is right
Answer general formula structure R1(- O-CO-O-CH2) and organic lithium salt ddCTP-Li3The molar ratio of lithium ion is 10:1, forms solution.
(3) solution is then heated to 120 DEG C of stirring 2h, obtains slurry, then slurry is uniformly coated on glass plate,
Finally, it is dried in vacuo 36h at 60 DEG C, obtains flexible solid lithium ion conductor.
Solid lithium ion conductors obtained by embodiment 3 have good flexibility；Tensile strength-strain curve as shown in fig. 7,
Its mechanical strength is up to 40MPa, and tensile strain rate is up to 225%.
Embodiment 4
(1) polymer using fluorobenzenesulfonimide lithium be grafted dimethyl polysiloxane, structural formula is as follows, wherein x:y=
2.6:1.It weighs the above polymer 0.2937g to be dissolved in 5.598g N-Methyl pyrrolidone, being sufficiently stirred keeps it completely molten
Solution.
(2) the LiFSI(relative molecular mass 187 that 0.51g contains imine is continuously added), corresponding general formula structure
R1(- Si (CH3)2- O-) it with the molar ratio of the lithium ion of organic lithium salt LiFSI is 5:1, form solution.
(3) solution is then heated to 85 DEG C of stirrings for 24 hours, obtains slurry.Finally, it is dried in vacuo for 24 hours, obtains at 65 DEG C
To flexible solid lithium ion conductor.
The flexible solid lithium ion conductor that embodiment 4 is obtained is as the binder of positive electrode, with acetylene black, ferric phosphate
Lithium is uniformly mixed according to mass ratio 15:10:75, obtains anode slice of lithium ion battery, group after rolling coated in drying on aluminium foil
The cycle performance for filling solid state battery is as shown in Figure 8.Initial discharge specific capacity is 149.8 mAh/g, circulation under room temperature, 0.2C
100 circle 124.7 mAh/g of residue, capacity retention ratio 83.3%, cyclical stability and service life significantly improve.
Claims (5)
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