CN108695547B - Organic-inorganic composite electrolyte membrane and battery with same - Google Patents
Organic-inorganic composite electrolyte membrane and battery with same Download PDFInfo
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- CN108695547B CN108695547B CN201810400093.5A CN201810400093A CN108695547B CN 108695547 B CN108695547 B CN 108695547B CN 201810400093 A CN201810400093 A CN 201810400093A CN 108695547 B CN108695547 B CN 108695547B
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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Abstract
The invention discloses an organic-inorganic composite electrolyte membrane, which comprises a double-layer structure consisting of a first layer and a second layer; the first layer and the second layer are both made of slurry comprising the following same components: an inorganic solid electrolyte, a lithium salt, a film-forming agent, a conductive lithium ion polymer, a plasticizer and a solvent; wherein the inorganic solid electrolyte content of layer one > the inorganic solid electrolyte content of layer two, the conductive lithium ion polymer content of layer one < the conductive lithium ion polymer content of layer two. The invention also discloses a battery containing the organic-inorganic composite electrolyte membrane. The organic-inorganic composite electrolyte membrane has good flexibility and high conductivity, meets different requirements of the anode and the cathode of the lithium ion battery on the membrane, can inhibit the growth of lithium dendrite and improves the comprehensive performance of the battery.
Description
Technical Field
The invention relates to the technical field of electrolyte membranes, in particular to an organic-inorganic composite electrolyte membrane; the invention also relates to the field of lithium batteries, in particular to a battery with an organic-inorganic composite electrolyte membrane.
Background
At present, liquid electrolyte is mostly adopted by commercial lithium ion batteries as a medium for transmitting lithium ions by a positive electrode and a negative electrode, but the liquid electrolyte has more and more obvious defects along with the safety requirements of the lithium ion batteries in the aspect of power electric vehicles. The reason is that the liquid electrolyte is easy to react and burn, so that great potential safety hazard is brought to the application of the lithium ion battery in the aspect of power electric vehicles. Aiming at the problems, the solid lithium ion electrolyte is used for replacing the traditional electrolyte, and the safety problem of the lithium ion battery can be better solved by preparing the all-solid lithium ion battery.
The solid electrolyte is classified into an inorganic solid electrolyte, a polymer solid electrolyte, and a composite polymer electrolyte. Among polymer electrolytes, PEO-based polymer solid electrolytes are the earliest and most studied all-solid polymer electrolytes. The lithium ion transmission principle is Li+Is not interrupted with oxygen atoms in ethylene oxide units on the amorphous PEO chain segmentComplexation and dissociation occur to achieve Li+Is being migrated. It has the advantages of light weight, good viscoelasticity and easy film formation, but also has narrow electrochemical window (less than 4V) and low room-temperature conductivity (about 10)-7s/cm) from the defect of 10 required for practical application-3The s/cm difference is large.
The inorganic solid electrolyte can maintain chemical stability over a wide temperature range relative to the polymer solid electrolyte, and thus the inorganic solid electrolyte-based battery has higher safety characteristics. The inorganic solid electrolyte has good stability, but has high ionic conductivity, wide electrochemical window, low cost and few materials which are easy to manufacture.
In this case, an organic-inorganic composite electrolyte membrane is produced. However, for the organic-inorganic composite electrolyte membrane, the physical and chemical properties of the materials are obviously different, which makes it difficult to achieve good combination of different materials when preparing the solid electrolyte membrane, and the prepared electrolyte membrane has defects easily, and is difficult to achieve the advantages of organic materials and inorganic materials at the same time, thus failing to meet the requirements of the positive electrode and the negative electrode of the battery at the same time and improving the comprehensive performance of the battery. For example, CN107346834A discloses a lithium salt-free added composite solid electrolyte membrane, which comprises a polymer matrix material and a fast ion conductor powder material, wherein the chemical formula of the fast ion conductor material is Li7-xLa3Zr2-xMxO12Wherein M is at least one of Al, Ta, Nb, W, Ga, Y and Te, and x is more than or equal to 0 and less than or equal to 1; further, CN105811002A discloses an all-solid-state secondary lithium battery composed of an organic polycarbonate polymer and an inorganic fast ion conductor compounded all-solid-state electrolyte, wherein the organic-inorganic compounded all-solid-state electrolyte is composed of a polycarbonate polymer, an inorganic fast ion conductor, a lithium salt, and a porous rigid support material. However, none of these techniques can solve the problems of poor flexibility and low conductivity of the organic-inorganic composite electrolyte membrane well.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide an organic-inorganic composite electrolyte membrane having good flexibility and electrical conductivity.
One of the technical solutions of the present invention is as follows:
an organic-inorganic composite electrolyte membrane, characterized in that it comprises a two-layer structure consisting of a first layer and a second layer; the first layer and the second layer are both made of slurry comprising the following same components: an inorganic solid electrolyte, a lithium salt, a film-forming agent, a conductive lithium ion polymer, a plasticizer and a solvent; wherein the inorganic solid electrolyte content of layer one > the inorganic solid electrolyte content of layer two, the conductive lithium ion polymer content of layer one < the conductive lithium ion polymer content of layer two.
Compared with the prior art, the structure has the following advantages: the content of the inorganic solid electrolyte in the first layer is high, one side of the first layer is in contact with the negative electrode, and the coating has high hardness and can inhibit the growth of lithium dendrites; the second layer has high polymer content and low solid electrolyte content, and has high flexibility, good adhesion, and reduced interface impedance. The related test results also show that the organic-inorganic composite electrolyte membrane has good flexibility and high conductivity, and simultaneously meets different requirements of the anode and the cathode of the lithium ion battery on the membrane, so that the all-solid-state lithium ion secondary battery with excellent comprehensive performance can be obtained.
Preferably, the mass ratio of the inorganic solid electrolyte, the lithium salt, the film forming agent, the conductive lithium ion polymer, the plasticizer and the solvent of the slurry used in the first layer is (20-50): (1-20): (1-10): 100.
Preferably, the mass ratio of the solid electrolyte, the lithium salt, the film forming agent, the lithium ion conducting polymer, the plasticizer and the solvent of the slurry used in the layer two is (5-30): (1-20): (1-10): 100.
Preferably, the inorganic solid-state electrolyte is any one or more of: li DE (PO)4)3(D is one of Ti, Zr, Si and Hf, E is one of Ti, Zr, Si and Ge), Li1+xGxJ2-x(PO4)3(0<x<1, G is one of Cr, Al and La, JIs Ti or Zr), Li1+xG0.2Lx-0.4M2.2-x(PO4)3(G is one of Cr, Al and La, L is one of Cr, Al and La, and M is one of Ti, Zr, Si and Hf). Further preferably, the inorganic solid electrolyte is Li Ti2(PO4)3、Li Zr2(PO4)3、Li Si2(PO4)3、Li Hf2(PO4)3、Li TiZr(PO4)3、Li TiSi(PO4)3、LiTiGe(PO4)3、Li SiGe(PO4)3、Li SiZr(PO4)3、Li1.3Cr0.3Ti1.7(PO4)3、Li1.2Zr1.9Ca0.1(PO4)3、Li1.5Al0.5Ti1.5(PO4)3、Li1.3La0.3Zr1.7(PO4)3、Li1.5Ca0.1La0.3Ti1.6(PO4)3、Li1.6Mg0.2B0.2Ge1.6(PO4)3、Li1.7Sr0.1Al0.5Ge1.4(PO4)3、Li2Zn0.2Sc0.3Zr1.5(PO4)3、Li1.4Sr0.1Gd0.2Zr1.7(PO4)3、Li1.7Ca0.2Al0.3Ti1.5(PO4)3、Li1.5Al0.5Ti1.0Ge0.5(PO4)3、Li1.4Al0.3Ti1.7Si0.1P2.9O12、LiGa0.2Ti1.6V0.2(PO4)3、LiCr0.3Ti1.4Ta0.3(PO4)3、Li1.5Al0.5Ge1.5Sb0.1P2.9O12、LiLa0.1Zr1.8Nb0.1(PO4)3、LiCr0.4Zr1.2Ta0.4(PO4)3、Li1.5Al0.5Ti1.5V0.1P2.9O12、Li1.3Al0.1Sc0.2Ti1.7(PO4)3、Li1.3Ca0.1Fe0.1Ti1.8(PO4)3Or Li2.2Al0.1Zn0.5Ti(PO4)3One or more of (a).
Preferably, the lithium salt is LiPF6、LiB(C2O4)2、LiClO4、LiBF4、LiCF3SO3One or more of (a).
Preferably, the film forming agent is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polypropylene oxide, polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyimide, cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, polyacrylic acid and polyacrylate.
Preferably, the conductive lithium ion polymer is one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, and polycarbonate.
Preferably, the plasticizer is one or more of polyvinyl alcohol, glycerol, ethylene glycol, dibutyl phthalate, ethyl carbonate, ethylene carbonate and propylene carbonate.
Preferably, the solvent is N, N dimethylformamide, and also one or more of N, N dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, ethanol, propanol, isopropanol, butanol, toluene, xylene, methyl ethyl ketone, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, methyl formate, chloroform, dimethyl carbonate, and diethyl carbonate.
The beneficial effects of the above technical scheme are as follows:
1) the organic-inorganic composite electrolyte membrane has a double-layer structure, wherein the content of inorganic solid electrolyte in the first layer is high, the content of polymer in the second layer is high, the content of solid electrolyte is low, and the organic-inorganic composite electrolyte membrane has good conductivity and flexibility;
2) the organic-inorganic composite electrolyte membrane has the advantages that the solid electrolyte content in one layer is high, one side of the layer is in contact with the negative electrode, the coating hardness is high, the growth of lithium dendrites can be inhibited, and the cycle performance is improved;
3) the organic-inorganic composite electrolyte membrane has high polymer content and low solid electrolyte content in the two layers, improves the flexibility of the electrolyte membrane, and has good cohesiveness, and one side of the layer is bonded with the anode, so that the interface impedance can be reduced, the internal resistance of the battery is reduced, and the requirements of all-solid-state lithium ion secondary batteries are met;
4) the organic-inorganic composite electrolyte membrane has the same double-layer structure components and different contents, is not easy to delaminate and has no excessive defects, and is beneficial to further reducing the internal resistance and prolonging the service life.
Another technical problem to be solved by the present invention is to provide a battery with low internal resistance and high safety performance.
The technical solution of the above technical problem is as follows: a battery having an organic-inorganic composite electrolyte membrane, which comprises a positive electrode, an electrolyte membrane and a negative electrode, the electrolyte membrane being the organic-inorganic composite electrolyte membrane of the present invention.
Compared with the prior art, the technical scheme has the following remarkable advantages and beneficial effects: by adopting the organic-inorganic composite electrolyte membrane with the double-layer structure, the first layer is in contact with the negative electrode, the coating has high hardness and can inhibit the growth of lithium dendrite, the second layer is in contact with the positive electrode, the adhesion with the positive electrode is good, the flexibility is good, the interface impedance can be reduced, the cycle performance and the safety performance are greatly improved, and the comprehensive performance of the battery is improved. .
Drawings
Fig. 1 is an electrochemical alternating current impedance spectrum (EIS) of a cell having a membrane 1 as an electrolyte membrane, in which the abscissa Z '(Ω) represents the real part of impedance, and the ordinate-Z' ″ (Ω) represents the imaginary part of impedance.
Fig. 2 is an electrochemical alternating current impedance spectrum (EIS) of a cell having the membrane 2 as an electrolyte membrane, in which the abscissa Z '(Ω) represents the real part of impedance, and the ordinate-Z' ″ (Ω) represents the imaginary part of impedance.
Fig. 3 is a cycle curve of a cell using membrane 1 as an electrolyte membrane.
Fig. 4 is a dc charge-discharge curve at room temperature of a battery using the membrane 1 as an electrolyte membrane.
Fig. 5 is a scanning electron micrograph of the side of film 1 facing the negative electrode after 900 cycles of the battery.
Fig. 6 is a scanning electron micrograph of the side of membrane 7 facing the negative electrode after 900 cycles of the cell.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
The raw materials and reagents involved in the present invention are commercially available.
The organic-inorganic composite electrolyte membrane and the composite electrolyte membrane have the same meaning.
The following examples are not provided to limit the scope of the present invention, nor are the steps described to limit the order of execution. Modifications of the invention which are obvious to those skilled in the art in view of the prior art are also within the scope of the invention as claimed.
Examples 1 to 32
An organic-inorganic composite electrolyte membrane consists of a first layer and a second layer which are tightly combined, wherein the first layer is prepared by a first slurry, and the second layer is prepared by a second slurry; both size one and size two included the same ingredients as follows: an inorganic solid electrolyte, a lithium salt, a film-forming agent, a conductive lithium ion polymer, a plasticizer and a solvent; the content of inorganic solid electrolyte in the first slurry is greater than that in the second slurry, and the content of conductive lithium ion polymer in the first slurry is less than that in the second slurry. During subsequent fabrication, only the solvent content will change, and the relative amounts of the other ingredients of layer one and layer two will not change. Namely, the inorganic solid electrolyte in the first slurry is taken as the main component, and the inorganic solid electrolyte in the dried layer I is still taken as the main component; and the conductive lithium ion polymer in the second slurry is used as the main component, and the conductive lithium ion polymer in the dried second layer is still used as the main component.
The organic-inorganic composite electrolyte membrane is prepared by the following method:
1) weighing various raw materials according to the formula ratio, and performing ball milling at the speed of 300 revolutions for 1 hour to obtain first slurry;
2) weighing various raw materials according to the formula ratio, and performing ball milling at the speed of 300 revolutions for 1 hour to obtain second slurry;
3) and (3) simultaneously coating the first slurry and the second slurry on a carrier (only one slurry is in contact with the carrier, and the other slurry is not in contact with the carrier) by a slide coating method, drying at the temperature of 70 ℃ for 5min, and then stripping the carrier to obtain a dry film with the total thickness of 15 mu m, namely obtaining the organic-inorganic composite electrolyte film (marked as film 1) in the embodiment 1.
The ingredients and specific ratios of the first slurry and the second slurry in examples 1 to 32 are shown in tables 1 and 2.
Table 1: components and proportions of first slurries of examples 1 to 32
Product testing
First, influence of inorganic solid electrolyte content on interfacial impedance of an organic-inorganic composite electrolyte membrane:
the test was conducted using the membrane 1 obtained in example 1 as a test group and the membrane 2 of comparative example 1 (the inorganic solid electrolyte content of layer one < the inorganic solid electrolyte content of layer two, the conductive lithium ion polymer content of layer one > the conductive lithium ion polymer content of layer two of the membrane 2, in contrast to the membrane 1) as a control group.
The preparation process of comparative example 1 is as follows: the membrane 2 also adopts a double-layer structure, the first layer opposite to the negative electrode is made of the same slurry I as the first layer in the embodiment 1, and the second layer opposite to the positive electrode adopts the slurry formula as follows: inorganic solid electrolyte lithium lanthanum zirconium oxygen (Li)1.3La0.3Zr1.7(PO4)3)4g of lithium salt lithium hexafluorophosphate (LiPF)6)1g of film forming agent polyvinylidene fluoride 1g, conductive lithium ion polymer polyethylene oxide 1g and plasticizer ethylene carbonate 0.1g are mixed in N-dimethylformamide 100g N, ball milled for 1 hour at 300 revolutions, coated and dried to form layer two.
The nickel-cobalt-manganese ternary material is used as a positive electrode, lithium is used as a negative electrode to assemble the battery, and the film 1 and the film 2 are used as electrolytes to manufacture the lithium battery, wherein the layer one is in contact with the negative electrode, and the layer two is in contact with the positive electrode. Electrochemical alternating current impedance spectroscopy (EIS) tests were performed on the assembled lithium battery, and it can be seen from fig. 1 and 2 that the contact resistance of the membrane 2 is greater than that of the membrane 1. From this, it was confirmed that the content of the inorganic solid electrolyte in the organic-inorganic composite film for a positive electrode was reduced, the adhesion of the coating layer to the positive electrode was increased, and the interface resistance was reduced.
Secondly, the influence of the content of the inorganic solid electrolyte on the flexibility of the organic-inorganic composite electrolyte membrane:
the inorganic solid electrolyte is lithium lanthanum zirconium oxygen (Li)1.3La0.3Zr1.7(PO4)3) The lithium salt is lithium hexafluorophosphate (LiPF)6) The film forming agent is polyvinylidene fluoride, the conductive lithium ion polymer is polyethylene oxide, the plasticizer is ethylene carbonate, the five raw materials are mixed in 100g of N, N dimethylformamide according to the mass ratio of 6:1:1: 0.1, 4:1:1:1:0.1, 2:1:1:1:0.1 and 1:1:1:0.1 respectively, ball milling is carried out at 300 revolutions for 1 hour, and the mixture is prepared into the single-layer organic-inorganic composite electrolyte membranes 3, 4, 5 and 6 respectively through a tape casting method (a gradient coating method can also be used). The organic-inorganic composite electrolyte membranes 3, 4, 5, 6 were tested for tensile strength and breakage rate, and the results are shown in table 3. As can be seen from table 3, as the solid electrolyte powder content decreases, the tensile strength of the organic-inorganic composite electrolyte membrane increases, the tensile fracture rate increases, and the flexibility of the organic-inorganic composite electrolyte membrane increases.
Table 3: tensile strength and fracture ratio of the organic-inorganic composite electrolyte membranes 3, 4, 5, 6
| Organic-inorganic composite electrolyte membrane | Tensile Strength (MPa) | Tensile breaking ratio |
| 3 | 4.3 | 18.10％ |
| 4 | 6.4 | 25.20％ |
| 5 | 7.8 | 38.90％ |
| 6 | 8.6 | 66.70％ |
Performance test of battery with double-layer organic-inorganic composite electrolyte membrane
(1) A cell having the double-layered organic-inorganic composite electrolyte membrane was prepared: the nickel-cobalt-manganese ternary material was used as the positive electrode, lithium was used as the negative electrode, the organic-inorganic composite electrolyte membrane 1 of example 1 was used as the electrolyte, and the side (layer one) having a high inorganic solid electrolyte content was opposite to the negative electrode.
(2) Electrochemical alternating current impedance spectroscopy (EIS) of the battery was tested, and as a result, as shown in fig. 1, the conductivity was calculated to obtain an ionic conductivity of 1.0 × 10 at room temperature-4S/cm。
(3) The cycle curve and the charge-discharge curve of the battery at room temperature are tested, and as shown in fig. 3 and fig. 4, the results show that the prepared all-solid-state battery has a relatively obvious charge-discharge platform, after 900 cycles, the capacity retention rate is 70%, and the coulomb efficiency of the battery is close to 100%.
And fourthly, testing the inhibition effect of the content of the inorganic solid electrolyte on the growth of the lithium dendrites:
the test was conducted with membrane 1 of example 1 and membrane 7 of comparative example 2 as a comparison.
The preparation process of comparative example 2 is as follows: membrane 7 was also made with a single layer structure using the same slurry number two as in example 1, with the slurry formulation: the solid electrolyte is lithium lanthanum zirconium oxygen (Li)1.3La0.3Zr1.7(PO4)3) The lithium salt is lithium hexafluorophosphate (LiPF)6) The film forming agent is polyvinylidene fluoride, the conductive lithium ion polymer is polyethylene oxide, and the plasticizer is ethylene carbonateEster, five raw materials in the mass ratio of 2:1: 0.1, in 100g N, N two methyl formamide mixture, 300 rotation ball milling for 1 hours, coating and drying to form the membrane 7.
The method comprises the steps of assembling a battery by taking a nickel-cobalt-manganese ternary material as a positive electrode and lithium as a negative electrode, assembling the battery by taking a film 1 and a film 7 as electrolyte films, disassembling the battery after circulating for 900 weeks at normal temperature, and observing one surfaces, facing the negative electrode, of the film 1 and the film 7 by using a scanning electron microscope. As can be seen from fig. 5 and 6, the surface of the membrane 1 is flat and smooth, the surface of the membrane 7 is rough, and a large amount of lithium dendrites grow, which indicates that the increase of the content of the inorganic solid electrolyte can effectively inhibit the growth of the lithium dendrites.
Claims (7)
1. An organic-inorganic composite electrolyte membrane, characterized in that it comprises a two-layer structure consisting of a first layer and a second layer; the first layer and the second layer are both made of slurry comprising the following same components: an inorganic solid electrolyte, a lithium salt, a film-forming agent, a conductive lithium ion polymer, a plasticizer and a solvent; wherein the content of the inorganic solid electrolyte in the first layer is more than that of the inorganic solid electrolyte in the second layer, and the content of the conductive lithium ion polymer in the first layer is less than that of the conductive lithium ion polymer in the second layer; the first layer is contacted with the negative electrode, and the second layer is contacted with the positive electrode; during preparation, the coating mode of the first layer and the second layer is slope flow coating;
the mass ratio of the inorganic solid electrolyte, the lithium salt, the film forming agent, the lithium ion conducting polymer, the plasticizer and the solvent of the slurry used in the first layer is (20-50): (1-20): (1-10): 100;
the mass ratio of the solid electrolyte, the lithium salt, the film forming agent, the conductive lithium ion polymer, the plasticizer and the solvent of the slurry used in the second layer is (5-30): (1-20): (1-10): 100;
the inorganic solid electrolyte is any one or more of the following: LiDE (PO)4)3Wherein D is one of Ti, Zr, Si and Hf, E is one of Ti, Zr, Si and Ge, Li1+xGxJ2-x(PO4)3Wherein x is more than 0 and less than 1, and G is one of Cr, Al and LaJ is Ti, Zr or Li1+x G0.2L x-0.4M2.2-x(PO4)3Wherein G is one of Cr, Al and La, L is one of Cr, Al and La, and M is one of Ti, Zr, Si and Hf.
2. The organic-inorganic composite electrolyte membrane according to claim 1, wherein the lithium salt is LiPF6、LiB(C2O4)2、LiClO4、LiBF4、LiCF3SO3One or more of (a).
3. The organic-inorganic composite electrolyte membrane according to claim 1, wherein the film-forming agent is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polypropylene oxide, polyethylene oxide, polyvinyl pyrrolidone, polyvinyl alcohol, polyimide, cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, polyacrylic acid, polyacrylate.
4. The organic-inorganic composite electrolyte membrane according to claim 1, wherein the conductive lithium ion polymer is one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, and polycarbonate.
5. The organic-inorganic composite electrolyte membrane according to claim 1, wherein the plasticizer is one or more of polyvinyl alcohol, glycerin, ethylene glycol, dibutyl phthalate, ethyl carbonate, ethylene carbonate, and propylene carbonate.
6. The organic-inorganic composite electrolyte membrane according to claim 1, wherein the solvent is one or more of N, N dimethylformamide, N dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, ethanol, propanol, isopropanol, butanol, toluene, xylene, methyl ethyl ketone, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, methyl formate, chloroform, dimethyl carbonate, and diethyl carbonate.
7. An organic-inorganic composite electrolyte membrane cell comprising a positive electrode, an electrolyte membrane and a negative electrode, wherein the electrolyte membrane is the organic-inorganic composite electrolyte membrane according to any one of claims 1 to 6.
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