CN107459647B - Polyimide type single ion conducting polymer with side chain grafted bis-sulfimide and application thereof - Google Patents

Polyimide type single ion conducting polymer with side chain grafted bis-sulfimide and application thereof Download PDF

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CN107459647B
CN107459647B CN201610387469.4A CN201610387469A CN107459647B CN 107459647 B CN107459647 B CN 107459647B CN 201610387469 A CN201610387469 A CN 201610387469A CN 107459647 B CN107459647 B CN 107459647B
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程寒松
孙玉宝
潘其云
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Salfa (Wuhan) New Energy Technology Co., Ltd
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Abstract

The invention discloses a polyimide type single ion conductive polymer with a side chain grafted with bissulfonylimide, a synthesis method and application thereof, wherein the room temperature ionic conductivity of a polymer electrolyte membrane formed by blending the polymer and PVDF-HFP is 0.10mS cm‑1And a maximum tensile strength in a dry state of 15.5MPa, and exhibits excellent electrochemical stability as an electrolyte-cum-separator of a gel-type lithium metal polymer secondary battery.

Description

Polyimide type single ion conducting polymer with side chain grafted bis-sulfimide and application thereof
Technical Field
The invention relates to a side chain grafted polyimide type single ion conducting polymer and application thereof, wherein a polyethylene maleic anhydride side chain grafted bissulfonyl imide polymer electrolyte shows excellent electrochemical stability in a metal lithium polymer secondary battery.
Background
The relative atomic mass of lithium metal is 6.94, the standard electrode potential is-3.045V (vs. nhe), and the theoretical specific capacity as a battery negative electrode is up to 3860 mAh/g. Lithium metal when matched with a suitable positive electrode can constitute a secondary battery with higher energy density and power density. The research of the lithium secondary battery started in the seventies of the twentieth century, but safety accidents were caused due to the high activity of metallic lithium and the formation of dendrites during the charge and discharge processes, which resulted in internal short circuits. Subsequently, the graphite negative electrode replaces metal lithium, so that the potential safety hazard is avoided to a great extent, and the large-scale application of the lithium ion secondary battery is brought. The demand of people on a high-specific-energy secondary power supply is gradually increased in the current society, and a graphite cathode with the specific capacity of 372mAh/g becomes one of bottlenecks in the development of lithium ion secondary batteries.
At present, there are two types of lithium ion secondary batteries using metallic lithium as a negative electrode, one is a room temperature inorganic all-solid-state metallic lithium secondary battery, and the other is an all-solid-state metallic lithium polymer secondary battery. The former is the development direction of future lithium batteries, but various performance indexes are to be optimized. The latter develops two types, one is a full solid state of double ions, namely polyoxyethylene is mixed with small molecular inorganic lithium salt, and the working temperature is higher than the glass transition temperature (>60 ℃); the other is the all solid state of single ion conduction, i.e. anion immobilization on polymer chains, which also cannot work at room temperature because ion conduction still requires thermal movement via polyoxyethylene chains. Although the addition of small molecules of plasticizer can improve the ionic conductivity of polymer electrolyte (gel-type polymer electrolyte), the problem of dendrite is inevitable for the dual-ion type lithium metal polymer secondary battery. The single ion conductive polymer electrolyte can avoid the dendrite problem caused by the introduction of plasticizer, because the single ion conduction can effectively reduce the concentration polarization, so that the current density on the surface of the electrode is averaged.
Inorganic all-solid-state lithium metal secondary batteries are still a few years away from commercialization, and gel single-ion conductive lithium metal polymer secondary batteries may be one of the more suitable options for the current development of high specific energy lithium metal secondary batteries. Although some literature reports gel single ion conducting lithium metal polymer secondary batteries, the number of cycles given is below 200 cycles. High stability and high ionic conductivity are technical difficulties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention designs a polyimide type single ion conducting polymer electrolyte with side chain grafted bissulfonyl imide and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme: a polyethylene maleic anhydride side chain grafted bissulfonylimide polymer has the following structural formula:
Figure BDA0001007523690000021
M＝H+,Li+,Na+or K+
R＝PhCF3,CF3,F,CN,PhX5(X＝F,Cl,Br)
Further, R is PhCF3，CF3F, CN or PhX5(X＝F，Cl，Br)。
Further, M is H+,Li+,Na+Or K+。
Further, the polar solvent may be N-methylpyrrolidone, dimethyl sulfoxide, N '-dimethylformamide, N' -dimethylacetamide, dimethyl carbonate or m-cresol.
Further, the temperature range of the heating dehydration polycondensation is 100-200 ℃.
The invention also provides a synthesis method of the unilateral para-amino substituted bissulfonyl imide micromolecule, which relates to two steps, namely firstly, the unilateral para-nitro substituted bissulfonyl imide micromolecule is obtained by the reaction of p-nitrobenzenesulfonamide and R-base sulfonyl chloride through Hinsberg, and secondly, the unilateral para-amino substituted bissulfonyl imide micromolecule is obtained by the chemical reduction of the para-nitro substituted bissulfonyl imide micromolecule.
Further, the reducing agent for reducing the para-nitro-substituted bissulfonimide micromolecules can be N2H4，H2，SnCl2Or reduced iron powder.
The invention also provides an application of the polyethylene maleic anhydride side chain grafted bis-sulfonyl imide polymer, which is prepared by grafting lithium salt and LiFePO4The lithium ion conductive polymer is mixed with conductive carbon powder to be used as a battery anode material, a composite membrane obtained by mixing polymer lithium salt and poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is used as a battery diaphragm and also used as an electrolyte, and metal lithium is used as a cathode material to obtain the gel type single-ion conductive metal lithium polymer secondary battery.
Further, the organic solvent selected for preparing the blend film may be N-methylpyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, or dimethylsulfoxide.
Further, the polymer lithium salt in the positive electrode is LiFePO4The mass ratio of the conductive carbon powder to the conductive carbon powder can be 1:7:2, 2:5:2, 2:6:2 or 3:6: 1.
Further, the mass ratio of the polymer lithium salt and the poly (vinylidene fluoride-co-hexafluoropropylene) in the blended film may be 0.5:1, 1:1, 1:1.5, or 1: 2.
The invention has the beneficial effects that: in the invention, the bis-sulfonyl imide micromolecules substituted by unilateral para-amino are connected to the side chain of the polyethylene maleic anhydride through polyimide chemical bonds, so that the polyethylene maleic anhydride modified bis-sulfonyl imide has excellent chemical stability and electrochemical stability; in addition, the distribution of the polymeric lithium salt in the positive electrode helps to construct an effective ion-conducting channel. The gel type single ion conduction metal lithium polymer secondary battery assembled by the polyethylene maleic anhydride side chain grafted bis-sulfonyl imide polymer electrolyte has better cycle performance.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 4-amino 4' -trifluoromethyl bis (benzenesulfonylimine), polyethylene maleic anhydride and side chain graft polymer lithium salt;
FIG. 2 is an infrared spectrum of 4-amino 4' -trifluoromethyl bis (benzenesulfonylimide), polyethylene maleic anhydride and side chain graft polymer lithium salt;
FIG. 3 is a thermogravimetric analysis of a lithium salt of a side-chain graft polymer;
FIG. 4 is a scanning electron micrograph of a side chain grafted polymer lithium salt blend film;
FIG. 5 is the tensile test results of a side chain grafted polymer lithium salt blended film;
FIG. 6 shows the electrochemical window test results of the side-chain grafted polymer lithium salt blend membrane;
FIG. 7 shows the results of the ionic conductivity test of the side-chain grafted polymer lithium salt blended membrane;
FIG. 8 shows the results of the ion transport number test of the side-chain grafted polymer lithium salt blend membrane;
fig. 9 is a result of a rate test of a gel type lithium metal polymer secondary battery;
fig. 10 is a result of cycle performance test of the gel type lithium metal polymer secondary battery.
Detailed Description
Example 1 this example synthesizes a polyethylene maleic anhydride side chain grafted bis-sulfonimide polymer by the following steps:
(1) synthesizing the bis-sulfimide substituted by the para-amino on one side according to the prior art, wherein the synthetic route is as follows:
Figure BDA0001007523690000041
the method specifically comprises the following steps:
(1.1) preparation of 4-Nitro-4' -trifluoromethylbisbenzenesulfonylimine
P-nitrobenzenesulfonamide and p-trifluoromethylbenzenesulfonyl chloride the ratio of 2: the feed ratio of 1 is stirred in alkaline solution at 90 ℃ for 12 h. Stirring was stopped, filtered and the filtrate was collected. Adding HCl into the filtrate to obtain white precipitate, filtering, recrystallizing the product, and drying for later use, wherein the yield is 40%.
(1.2) preparation of 4-amino-4' -trifluoromethylbisbenzenesulfonylimide
Step 1.1 product is dissolved in 80mL dichloromethane solution, poured into stannous chloride and hydrochloric acid methanol solution, and stirred for reaction for 4h at 40 ℃. The reaction mixture was filtered and the precipitate was washed with a mixed solution of methanol and dichloromethane (20:80, v/v) to give the pure product, which was dried under vacuum at 60 ℃ for use in 80% yield.
(2) The synthesis of the polyethylene maleic anhydride side chain grafted bissulfonyl imide polymer comprises the following synthetic route:
Figure BDA0001007523690000051
the specific synthetic steps are as follows:
weighing the polyethylene maleic anhydride and the product (3) according to the stoichiometric ratio into a 50mL two-neck flask, then adding m-cresol and a plurality of drops of isoquinoline, and reacting at 120 ℃ for 10h under the argon atmosphere, and then reacting at 200 ℃ for 12 h. The reaction product was poured into toluene to precipitate a solid product, which was then washed with methanol to obtain the product. And (4) drying for later use after lithium ion exchange.
The nuclear magnetic characterization results of the polyethylene maleic anhydride, the 4-amino 4' -trifluoromethyl bis-benzenesulfonylimine and the side chain grafted bis-sulfonylimine polymer lithium salt are as follows:
by d6DMSO dissolves the raw materials and products, and the nuclear magnetic hydrogen spectrum detects the structures of the raw materials and the products, and the results are shown in figure 1. 4-amino 4-Nuclear magnetic parameters of trifluoromethyl bisbenzenesulfonylimide (shown in fig. 1 (a)):1H NMR(400MHz,d6-DMSO) δ 7.86(d,2H), δ 7.77(d,2H), δ 7.55(d,2H), δ 6.92(d, 2H). Four groups of double peaks appear between 6.8 and 8.0, the area integral ratio is 1.00:0.98:0.97:0.99, which is close to 1:1:1:1, and the four groups of double peaks correspond to four groups of hydrogen in different chemical environments, such as'd', 'c', 'b', 'a' marked on the target molecule (3) in the figure 1 (a).
Nuclear magnetic parameters of polyethylene maleic anhydride (shown in fig. 1 (b)):1H NMR(400MHz,d6-DMSO) delta 3.04(s,2H), delta 2.05-1.76 (m, 5.6H). Two groups of peaks appear between 3.2 and 1.4, the area integral ratio is 1.00:2.80, and the two groups of peaks correspond to hydrogen in two different chemical environments, namely 'a' and 'b' marked on the target molecule (4) in the figure 1 (b). Theoretically, the ratio of the area integrals of the two groups of hydrogen "a" and "b" should be 1:2, but here the hydrogen not on the anhydride, i.e. "b" hydrogen, is somewhat larger in area, since the ratio of ethylene to butenedioic anhydride polymerized is not strictly 1:1, here it is evident that there is a slight excess of ethylene.
Nuclear magnetic parameters of the side chain grafted lithium bis-sulfonimide polymer (shown in fig. 1 (c)):1H NMR(400MHz,d6-DMSO) delta 7.81(d,4H), delta 7.26(d,4H), delta 3.00-0 (m, 14H). Two groups of hydrogen peaks appear between 9 and 6.8, corresponding to hydrogen on a benzene ring of a side chain, and a group of broad peaks and a plurality of miscellaneous peaks (delta 2.5, 1.22 and 0.84) are superposed between 3 and-0.5, corresponding to hydrogen on a main chain of a polymer. The hydrogen peak in this interval is first subjected to peak-splitting fitting (as shown in the fitting result diagram inserted at the left side of fig. 1 (c)) and the portion corresponding to the hetero peak is subtracted, so that the proportion of the main chain hydrogen is 70.15%. The benzene hydrogen and alkane hydrogen were integrated separately from the same baseline to give a ratio of 1: 1.76. Theoretically, if one acid anhydride corresponds to one graft molecule, the ratio of the integrated areas of the benzene hydrogen and the alkane hydrogen should be 8:7.6, and the actual ratio should be 4.32:7.6, so that the actual grafting ratio is estimated to be 54%. That is, on average, one bis-sulfonimide small molecule is grafted per two anhydrides, corresponding to the molecular formula shown on the right side of FIG. 1 (c).
Polyethylene maleic anhydride, 4-amino-4' -trifluoromethylbisbenzenesulfonylimide and side chainThe infrared characterization result of the grafted bis-sulfonimide polymer lithium salt is shown in fig. 2: after chemical grafting, the absorption peak of the sulfone in the grafted polymer is found to be 1402cm-1And an absorption peak of 1325-1059 cm of trifluoromethyl-1In addition, there are still absorption peaks 1716 and 1595cm for the anhydride-1Relative to the original 1855 and 1780cm-1A red shift occurs. The presence of the anhydride absorption peak also indicates that the grafting yield is not 100%, which is compatible with the results of the quantitative nuclear magnetic analysis.
The thermogravimetric analysis result of the side chain grafted bis-sulfonyl imide polymer lithium salt is shown in figure 3, and the polymer loses 5% weight at 325 ℃, and shows good thermal stability.
(3) Preparation and electrochemical performance of the polyethylene maleic anhydride side chain grafted bissulfonyl imide polymer electrolyte blend membrane.
Weighing a certain amount of polymer lithium salt and poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) according to the mass ratio of 1.5:1, dissolving in an N-methylpyrrolidone solution, sucking a certain amount of solution, spreading on flat glass, and evaporating the solvent to dryness to obtain the blend membrane.
The scanning electron microscope test result is shown in fig. 4, one side close to the glass is very dense, a plurality of nano-scale small holes are distributed on the surface of one side close to the air, and the section part does not have any hole structure, which indicates that the obtained electrolyte membrane is dense.
The electrolyte membrane was cut into a width of 1cm and a length of 15cm, and subjected to a tensile test on an electronic tensile machine, and as a result, as shown in FIG. 5, the elongation was 4.5% and the tensile strength was 16 MPa.
The electrolyte membrane was cut into a circular sheet having a diameter of 1.5cm, vacuum-dried, wetted with an EC/PC (1/1, v/v) mixed solution in a glove box, attached to a lithium metal sheet and then placed in a stainless steel jig. The cyclic voltammetry was measured using an electrochemical workstation after removal, and the results are shown in FIG. 6. When the potential is higher than 4V, the current is slightly increased, but the current does not tend to increase continuously.
The ionic conductivity was measured using ac impedance. A dried electrolyte membrane 1.5cm in diameter was soaked with EC/PC (1/1, v/v) and placed in stainless steelIn a steel jig. After being taken out, the alternating current impedance is tested by an electrochemical workstation, the frequency is from 1MHz to 100Hz, and the potential step amplitude is +/-10 mV. Fitting the impedance curve, extrapolating to the intersection of the high frequency and the real axis, calculating the ionic conductivity by substituting the abscissa of the intersection point, i.e. the ionic resistance of the membrane, into the following formulalAnd R and A represent the thickness, ionic resistance and area of the film, respectively. The ionic conductivities at different temperatures were tested and the results are shown in fig. 7. The room temperature ionic conductivity is 0.10mS cm-1And an ionic conductivity of 0.13mS · cm at 30 DEG C-1And an ionic conductivity of 0.17mS · cm at 40 DEG C-1And an ionic conductivity of 0.22mS · cm at 50 DEG C-1And an ionic conductivity of 0.23mS · cm at 60 DEG C-1Ion conductivity at 70 ℃ of 0.32mS · cm-1Ion conductivity at 80 ℃ of 0.35mS cm-1。
Figure BDA0001007523690000071
The ion transport number is measured by using a timing current in combination with an alternating current impedance. The dried electrolyte membrane, 1.5cm in diameter, was sandwiched between two lithium metal plates, soaked in EC/PC (1/1, v/v) and placed in a stainless steel jig. After being taken out, an electrochemical workstation is used for testing alternating current impedance, the frequency is from 1MHz to 100Hz, and the potential step amplitude is +/-5 mV; then applying constant potential of 10mV, and recording the change of current along with time; after about 7000 seconds, the same AC impedance test was again performed, and the results are shown in FIG. 8. The lithium ion transport number is calculated according to the following formula, where Δ V is the applied potentiostatic potential, I0And ISIs the initial current and steady state current, R0And RSAre the initial interface resistance and the steady state interface resistance. The calculation result was 0.92, close to 1.
Figure BDA0001007523690000072
Example 2: this example uses the polyethylene maleic anhydride side-chain grafted bis-sulfonimide polymer lithium salt prepared in example 1 mixed with poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)The obtained composite membrane is used as a diaphragm of a battery and also used as an electrolyte, and polymer lithium salt and LiFePO are used4Mixing the lithium ion conductive lithium ion polymer with conductive carbon powder to be used as a battery anode material, and using metal lithium as a cathode material to obtain a gel type single ion conductive lithium metal polymer secondary battery, which comprises the following steps:
preparation of the positive electrode: the active substance, the active carbon and the polymer lithium salt are weighed according to the mass ratio of 6:2:2, are added with N-methyl pyrrolidone and then are uniformly mixed, and are coated on a metal aluminum foil by a scraper, and then are dried, cut into pieces and dried in vacuum.
Assembling the battery: the positive plate, the PP film and the metallic lithium plate are placed in a 2025 stainless steel battery shell, added with EC/PC (1/1, v/v) for wetting, and then packaged.
The results of the rate test of the battery at room temperature are shown in FIG. 9, and the specific capacity of 0.2C is 123mAh g-1The specific capacity of 0.4C was 114mAh g-1The specific capacity of 0.6C was 107mAh g-1And a specific capacity of 103 mAh.g at 0.8C-1And the specific capacity of 1.0C is 100 mAh.g-1And the specific capacity of 2.0C is 86 mAh.g-1And the specific capacity of 3.0C is 77 mAh.g-1And a specific capacity of 4.0C of 71 mAh.g-1And a specific capacity of 5.0C of 65 mAh.g-1. The cycle test results are shown in FIG. 10, in which more than 1000 cycles were tested at 1C rate, and the capacity was maintained at 100mAh g-1And is very stable.

Claims (12)

1. The polyimide type single ion conducting polymer with the side chain grafted with bissulfonylimide is characterized in that the structural formula is as follows:
Figure FDA0002246039350000011
M＝H+,Li+,Na+or K+
R＝PhCF3,CF3,F,CN,PhXkK has a value of 1,2,3,4,5, X is independently selected from F, Cl, Br; the ratio of m to n is 2: 1 to 1: 2.
2. The polyimide-type single ion conducting polymer having a bis-sulfonimide grafted on a side chain according to claim 1, wherein: the ratio of m to n is 1:1.
3. A method for synthesizing a polyimide type single ion conducting polymer of side chain grafted bis-sulfonimide as claimed in claim 1 or 2, which comprises subjecting polyethylene maleic anhydride and bis-sulfonimide substituted with one side para-amino group to thermal dehydration polycondensation in a polar solvent, wherein the reactive functional groups are anhydride and amino groups, respectively, and then performing cation exchange, and the cation is proton, lithium ion, sodium ion or potassium ion.
4. The synthesis method according to claim 3, wherein R is trifluoromethyl, p-trifluoromethylbenzene, fluorine, nitrile group or 2,3,4,5, 6-pentahalogenobenzene, wherein the halogen is one of F, Cl and Br.
5. The method of claim 3, wherein the polar solvent is N-methylpyrrolidone, m-cresol, N, N '-dimethylformamide, N, N' -dimethylacetamide, dimethyl carbonate, or dimethylsulfoxide.
6. The synthesis method according to claim 3, wherein the temperature range of the heating dehydration polycondensation is 100-300 ℃.
7. A polymer film comprising the side-chain grafted bis-sulfonimide polyimide-type single ion conducting polymer as claimed in claim 1 or 2.
8. The polymer film of claim 7, further comprising poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), both dissolved in a polar solvent to provide a polymer blend film upon evaporation of the solvent.
9. The polymer membrane of claim 8, wherein the polar solvent is N-methylpyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, or dimethylsulfoxide.
10. Use of a polymer film according to any one of claims 7 to 9 as a battery separator.
11. The use of the polymer film according to claim 10, wherein the battery comprises lithium iron phosphate as a positive electrode material, lithium metal as a negative electrode material, and ethylene carbonate/propylene carbonate as a plasticizer.
12. Use of a polyimide-type single ion conducting polymer with side chain grafted bis-sulfonimide according to claim 1 or 2 in the preparation of a lithium ion battery.
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