CN115764153A - Polyolefin-based lithium ion battery composite diaphragm and preparation method and application thereof - Google Patents
Polyolefin-based lithium ion battery composite diaphragm and preparation method and application thereof Download PDFInfo
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- CN115764153A CN115764153A CN202211294416.XA CN202211294416A CN115764153A CN 115764153 A CN115764153 A CN 115764153A CN 202211294416 A CN202211294416 A CN 202211294416A CN 115764153 A CN115764153 A CN 115764153A
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Abstract
The invention belongs to the technical field of lithium ion battery diaphragms, and particularly relates to a polyolefin-based lithium ion battery composite diaphragm and a preparation method and application thereof. The method comprises the following steps: dissolving potassium permanganate in deionized water, and adding a transition metal salt to obtain a uniform solution; and floating the polyolefin base film in the solution, taking out the polyolefin base film after reaction, washing with water, and drying to finally obtain the composite diaphragm. The invention realizes the modification of the ultrathin metal-doped manganese dioxide nanorod network layer on the surface of the polyolefin base film by a simple in-situ chemical growth method. The introduction of metal doping synchronously realizes the regulation of material morphology and the construction of oxygen vacancy. The prepared composite diaphragm is applied to the lithium-sulfur battery, so that the chemical affinity and catalytic activity to polysulfide are effectively improved, the transmission efficiency of lithium ions is ensured, and the electrochemical performance of the lithium-sulfur battery is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery diaphragms, and particularly relates to a polyolefin-based lithium ion battery composite diaphragm and a preparation method and application thereof.
Background
With the development of mobile devices and new energy automobiles, energy storage systems put higher demands on energy density. However, lithium ion batteries cannot meet the high energy requirements of electric vehicles and next generation energy storage. This is because conventional lithium ion batteries rely on intercalation-type electrode materials, and lithium ions can only be topologically intercalated at specific locations, which limits their charge storage capacity and energy density. Therefore, exploring new battery chemistries beyond current lithium ion batteries is critical to the future of sustainable development. Therefore, the material has high theoretical capacity density (1675 mAh g) -1 ) Energy density (2600 Wh. Kg) -1 ) The lithium-sulfur battery is expected to become a next generation high energy storage battery after entering the field of vision of people. However, the lithium sulfur battery still has some problems such as volume expansion of sulfur, poor conductivity of sulfur, and dissolution of polysulfide. In particular, the dissolution of polysulfides, which diffuse into the electrolyte and then shuttle across the separator by concentration diffusion and electric field effects, severely affects cell performance and cycle life, thereby limiting their development.
In recent years research, it has become common to design various non-polar or polar materials to complex with sulfur to suppress the "shuttling effect" of polysulfides. The research on the modification of the membrane as a new strategy has attracted the attention of researchers due to the relative simplicity of the synthesis process. At present, metal oxide, which is a polar material, is widely used for modification of a separator due to its strong chemical adsorption capacity to polysulfide. However, most metal oxide modified membranes are physically coated, the preparation method comprises the steps of uniformly mixing metal oxide, carbon material, binder and other auxiliaries to prepare slurry, and finally coating the slurry on the surface of a commercial diaphragm substrate. This physical coating of the separator inevitably presents a series of challenges: (i) The step of coating the slurry is tedious and long, which is very unfavorable for actual industrial production; (ii) The use of an auxiliary agent such as a binder inevitably reduces the content of the metal oxide per unit area, so that the active sites are not exposed enough, thereby affecting the adsorption effect on polysulfide; (iii) The weak adhesion between the coating and the commercial diaphragm can cause unstable structure, so that the modified layer is easy to peel off from the commercial diaphragm, and the long cycle performance of the battery is influenced; (iv) The coating is easy to form a close-packed structure, which results in the reduction of lithium ion transmission efficiency and the strong adsorption of the metal oxide and polysulfide can further block the lithium ion transmission channel by polysulfide, thereby reducing the reaction kinetics of the lithium-sulfur battery. Therefore, transforming the interaction between the metal oxide modification layer and the commercial separator by a simple in-situ chemical growth method is one of the important means to solve the above-mentioned problems to improve the electrochemical performance of the lithium-sulfur battery.
Disclosure of Invention
The invention provides a preparation method of a polyolefin-based lithium ion battery composite diaphragm, the composite diaphragm obtained by the method and the application of the composite diaphragm, aiming at solving the problems and the defects existing in the physical coating mode of a metal oxide modified diaphragm. The invention realizes the modification of the ultrathin metal-doped manganese dioxide nanorod network layer on the surface of the polyolefin base film by a simple in-situ chemical growth method. The introduction of metal doping synchronously realizes the regulation of material morphology and the construction of oxygen vacancy. The prepared composite diaphragm is applied to the lithium-sulfur battery, so that the chemical affinity and catalytic activity to polysulfide are effectively improved, the transmission efficiency of lithium ions is ensured, and the electrochemical performance of the lithium-sulfur battery is remarkably improved. Meanwhile, the composite diaphragm obtained by in-situ chemical growth has excellent thermal stability, and the safety of the lithium-sulfur battery is effectively ensured.
The technical scheme provided by the invention is as follows:
a preparation method of a polyolefin-based lithium ion battery composite diaphragm comprises the following steps:
dissolving potassium permanganate in deionized water, and adding a proper amount of transition metal salt to obtain a uniform solution; and floating the polyolefin base film in the solution, taking out the polyolefin base film after reaction, washing with water, and drying to finally obtain the composite diaphragm.
Based on the technical scheme:
the preparation of the polyolefin-based lithium ion battery composite diaphragm adopts a simple one-step method to realize metal doping, further synchronously regulate and control the material appearance and construct oxygen vacancies, and realize the polyolefin-based lithium ion battery composite diaphragm. The ultrathin nanorod network layer obtained by in-situ chemical growth design has the characteristics of high electrolyte permeability, high ion transmission rate, excellent thermal stability and the like, and meanwhile, the electronic structure of the metal oxide is adjusted by introducing abundant oxygen vacancies to realize the optimization of adsorption activity and catalytic activity.
The composite diaphragm of the polyolefin-based lithium ion battery composite diaphragm is used as a lithium sulfur battery diaphragm, shows synergistic adsorption and catalysis effects on polysulfide, improves the adsorption effect on polysulfide and accelerates the redox reaction kinetics of polysulfide conversion; the nanorod network structure modification layer avoids the accumulation of active substances and ensures a transmission channel of lithium ions in long circulation; meanwhile, the in-situ chemical growth method avoids the problems of complicated and long experimental steps, low content of metal oxide in unit area, unstable structure of a modification layer and the like, thereby remarkably improving the cycle stability of the lithium-sulfur battery.
Based on the technical scheme:
specifically, the transition metal salt includes, but is not limited to: any one of metal cobalt salt, metal zinc salt, metal iron salt, metal nickel salt, metal copper salt or metal magnesium salt or any one of hydrates thereof.
Specifically, the polyolefin-based film includes but is not limited to: a single-layer polyethylene diaphragm, a single-layer polypropylene diaphragm, and a multi-layer composite film of polyethylene and polypropylene (e.g., a polypropylene/polyethylene double-layer film, a polypropylene/polypropylene double-layer film, a polypropylene/polyethylene/polypropylene three-layer composite film, etc.). These materials can be selected from the prior art.
In particular toThe KMnO 4 The concentration of the solution is 0.1M to the saturation concentration; the ratio of the amount of the transition metal salt to the amount of the potassium permanganate is 1 (1-30).
Specifically, the reaction time is 30 min-7 d, the reaction temperature is 25-60 ℃, and the reaction mode is standing or ultrasonic.
Specifically, the thickness of the obtained polyolefin-based lithium ion battery composite membrane is 300-400 nm; the drying mode is normal temperature and 8-12 h.
The invention provides the composite diaphragm prepared by the method.
The composite diaphragm has the characteristics of simple preparation steps, stable structure, ultrathin modification layer, high ion transmission, excellent catalytic activity and the like, so that the composite diaphragm can be used in the fields of lithium-sulfur batteries, lithium batteries, supercapacitors and photocatalysis.
The nanorod network structure modification layer in the composite diaphragm material avoids the accumulation of active substances, ensures a transmission channel of lithium ions in long circulation, and can be used for lithium-sulfur batteries, lithium batteries and super capacitors based on the convex performance in the aspect.
The composite diaphragm material is introduced with abundant oxygen vacancies to adjust the electronic structure of the metal oxide to realize the optimization of the adsorption activity and the catalytic activity, and can be used in the field of photocatalysis based on the salient performance in the aspect.
Further, the composite diaphragm is used as a lithium-sulfur battery diaphragm.
The invention has the following advantages and positive effects:
1. according to the invention, through a simple one-step method, the polyolefin-based lithium ion battery composite diaphragm is free from using auxiliary agents such as a binder and the like, so that the problems of low content of metal oxide in unit area, weak adhesion between a modification layer and a commercial diaphragm and the like are avoided;
2. according to the invention, by introducing metal doping, on one hand, the growth morphology of manganese dioxide on the surface of the polyolefin base film is regulated, so that an ultrathin nanorod network layer structure with uniform growth is obtained, and a transmission channel of lithium ions in long circulation is ensured; on the other hand, the electronic structure of the metal oxide is adjusted by constructing abundant oxygen vacancies to realize the optimization of the adsorption activity and the catalytic activity;
3. the composite diaphragm obtained by in-situ chemical growth has excellent thermal stability, and the safety of the lithium-sulfur battery is effectively ensured;
4. the preparation method disclosed by the invention is simple in preparation process, does not need long and complicated experimental steps, has the characteristics of mild reaction conditions, controllable process, high universality and the like, and is easy to realize industrial mass production.
Drawings
FIG. 1 shows SEM images of a composite separator and a polypropylene separator in example 1 of the present invention;
FIG. 2 shows Fourier infrared spectra of the composite membrane and the polypropylene membrane in example 1 of the present invention;
fig. 3 shows an electron paramagnetic resonance spectrum and a structural stability test chart of the composite separator in example 1 of the present invention;
fig. 4 shows an electrolyte contact angle test chart of the composite separator and the polypropylene separator in example 1 of the present invention;
fig. 5 shows a thermal stability test chart of the composite separator and the polypropylene separator in example 1 of the present invention;
FIG. 6 shows a comparison graph of polysulfide permeation experiments for composite membranes and polypropylene membranes in example 1 of the present invention;
FIG. 7 is a graph showing the cyclic voltammogram and capacity fade after 200 cycles of the composite membrane and the polypropylene membrane in example 1 of the present invention;
FIG. 8 shows a scanning electron microscope image and an electrolyte contact angle test image of a comparative composite separator in comparative example 1 of the present invention;
FIG. 9 is a flow chart of the manufacturing method of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
It will be understood that when an element or component is referred to as being "connected," "positioned" or "coupled" to another element or component, it can be directly on the other element or component or intervening elements or components may also be present. The terms "left", "right", "upper", "lower" and the like as used herein are for illustrative purposes only.
Example 1
The embodiment describes the polyolefin-based lithium ion battery composite membrane (hereinafter referred to as composite membrane) and the preparation method thereof in detail, and comprises the following steps:
dissolving 6.3g of potassium permanganate in 200mL of deionized water to form a uniform potassium permanganate solution, and then adding 11.6g of cobalt nitrate hexahydrate to obtain a uniform solution; floating a polypropylene diaphragm (obtained by market purchase) in the solution, carrying out ultrasonic reaction for 1h at 60 ℃, taking out the polypropylene diaphragm, washing with water, and drying for 12h at normal temperature to finally obtain the composite diaphragm.
Scanning electron micrographs of the composite membrane and the polypropylene membrane prepared in the example 1 are shown in fig. 1, the polypropylene membrane (part a in fig. 1) presents an original irregular pore structure, and the composite membrane (part b in fig. 1) presents a nanorod network structure;
the Fourier infrared spectrogram of the composite membrane and the polypropylene membrane prepared in the embodiment 1 is shown in FIG. 2, and the Fourier infrared spectrogram of the composite membrane is 1680cm -1 And 1671cm -1 A new peak appears, which indicates that a strong chemical bond (C = O) is formed between the manganese dioxide and the oxygen-containing group in the polypropylene diaphragm, thereby indicating that the ultrathin metal-doped manganese dioxide nanorod network layer successfully grows on the surface of the polyolefin base film in an in-situ chemical manner;
the electron paramagnetic resonance spectrum of the composite diaphragm prepared in this example 1 is shown in a part a of fig. 3, and a strong electron paramagnetic resonance signal is observed at a g value of 2.002, indicating the successful introduction of a large number of oxygen vacancies; the structural stability test chart of the composite diaphragm is shown in part b in fig. 3, the composite diaphragm does not fall off after the test, and the fact that the modification layer and the polypropylene diaphragm have strong adhesive force shows that the composite diaphragm has good structural stability;
the contact angle test chart of the electrolyte of the composite diaphragm and the polypropylene diaphragm prepared in the embodiment 1 is shown in fig. 4, the contact angle of the composite diaphragm and the electrolyte is 24.5 degrees, the contact angle of the diaphragm and the electrolyte is 49.4 degrees, which indicates that the nanorod network structure is beneficial to enhancing the permeability of the electrolyte, thereby promoting the transmission of lithium ions;
the thermal stability test chart of the composite diaphragm and the polypropylene diaphragm prepared in the embodiment 1 is shown in fig. 5, the polypropylene diaphragm is severely shrunk along with the rise of the temperature, and the composite diaphragm is only slightly curled after being treated and has no obvious deformation, which indicates that the composite diaphragm has good thermal stability;
comparison of polysulfide permeation experiments of the composite membrane and the polypropylene membrane prepared in example 1 is shown in fig. 6, and for the composite membrane (part a in fig. 6), the color of the solution on the right side does not change significantly within 24h, which indicates that the composite membrane has a higher active substance unit area content, exposes more active sites, and has a stronger adsorption capacity for polysulfide so as to hinder the shuttle effect. In contrast, for the polypropylene separator (part b in fig. 6), some polysulfides were observed within 8 h. Then at 16h, almost all of the solution on the right became tan indicating that the polysulfide could be easily shuttled through the polypropylene septum.
The experimental method of the polysulfide penetration experiment is as follows: the permeation experiment was carried out using an H-quartz tube consisting of two identical glass vessels with a 17mm hole in the middle and connected in a clamp fashion. For testing, a modified layer or commercial polypropylene membrane was placed over and completely covered the hole. Then 40mL of 0.05M Li was added to the left H-shaped quartz tube 2 S 6 To the right, 40mL of DME/DOL (v/v = 1:1) solution was added. Finally, an H-shaped quartz tube was placed on a horizontal surface and the course of the color change was recorded by a camera.
In this embodiment 1, a cyclic voltammetry curve of a button cell (CR 2016) obtained by respectively assembling a composite membrane and a polypropylene membrane is shown in a part a of fig. 7, where a cathode/anode peak of the composite membrane button cell has significant positive/negative shift and reaches a maximum response peak current, indicating that a nanorod network structure and abundant oxygen vacancies of the composite membrane exhibit synergistic adsorption and catalysis effects on polysulfides, thereby improving oxidation-reduction reaction kinetics of polysulfides and utilization rate of sulfur; the graph of the capacity fading condition of the button cell (CR 2016) obtained by respectively assembling the composite diaphragm and the polypropylene diaphragm under the condition of 0.5C and 200 cycles is shown in part b in fig. 7, wherein the capacity retention rate of the composite diaphragm button cell is as high as 84.4%, while the capacity retention rate of the polypropylene diaphragm button cell is only 47.2%, which shows that the composite diaphragm button cell has better capacity retention rate and provides possibility for realizing a stable lithium-sulfur cell.
Example 2
The embodiment describes the polyolefin-based lithium ion battery composite membrane (hereinafter referred to as composite membrane) and the preparation method thereof in detail, and comprises the following steps:
dissolving 12.6g of potassium permanganate in 200mL of deionized water to form a uniform potassium permanganate solution, and then adding 1.2g of cobalt nitrate hexahydrate to obtain a uniform solution; floating the polypropylene diaphragm in the solution, standing at 40 ℃ for reaction for 2d, taking out the polypropylene diaphragm, washing with water, and drying at normal temperature for 8h to finally obtain the composite diaphragm.
Example 3
The embodiment describes the polyolefin-based lithium ion battery composite membrane (hereinafter referred to as composite membrane) and the preparation method thereof in detail, and comprises the following steps:
dissolving 6.3g of potassium permanganate in 200mL of deionized water to form a uniform potassium permanganate solution, and then adding 11.6g of nickel nitrate hexahydrate to obtain a uniform solution; floating the polypropylene diaphragm in the solution, carrying out ultrasonic reaction for 1h at 60 ℃, taking out the polypropylene diaphragm, washing with water, and drying for 8h at normal temperature to finally obtain the composite diaphragm.
Example 4
This example describes a polyolefin-based lithium ion battery composite membrane (hereinafter referred to as a composite membrane) and a preparation method thereof in detail, including the following steps:
dissolving 12.6g of potassium permanganate in 200mL of deionized water to form a uniform potassium permanganate solution, and then adding 11.9g of zinc nitrate hexahydrate to obtain a uniform solution; floating the polypropylene diaphragm in the solution, standing at 30 ℃ for reaction for 5d, taking out the polypropylene diaphragm, washing with water, and drying at normal temperature for 8h to finally obtain the composite diaphragm.
Comparative example 1
The preparation method (hereinafter referred to as composite diaphragm) for chemically growing the manganese dioxide layer on the surface of the polyolefin base film in situ and the preparation method thereof are explained in detail, and comprise the following steps:
dissolving 6.3g of potassium permanganate in 200mL of deionized water to form a uniform potassium permanganate solution, floating the polypropylene diaphragm in the solution, carrying out ultrasonic reaction at 60 ℃ for 1h, taking out the polyolefin base film, washing with water, and drying at normal temperature for 12h to finally obtain the comparative composite diaphragm.
A scanning electron microscope image of the comparative composite separator prepared in comparative example 1 is shown in part a in fig. 8, and the manganese dioxide layer grows unevenly on the surface of the polyolefin base film, presenting an uneven blocky structure; the contact angle test chart of the electrolyte of the comparative composite diaphragm is shown in part b in fig. 8, the contact angle of the comparative composite diaphragm and the electrolyte is 34.3 degrees, which shows that the uneven block structure is not beneficial to the permeation of the electrolyte, and the lithium ion transmission performance is reduced.
The foregoing is merely a preferred embodiment of this invention and is not intended to limit the invention in any manner; those skilled in the art can readily practice the invention as shown and described in the drawings and detailed description herein; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the polyolefin-based lithium ion battery composite membrane is characterized by comprising the following steps of:
1) Dissolving potassium permanganate in deionized water, and adding a transition metal salt to obtain a uniform solution;
2) Floating the polyolefin base membrane in the solution obtained in the step 1), reacting, taking out the polyolefin base membrane after reaction, washing with water, and drying to finally obtain the composite diaphragm.
2. The method for preparing the polyolefin-based lithium ion battery composite separator according to claim 1, wherein in the step 1), the transition metal salt includes but is not limited to: any one of metal cobalt salt, metal zinc salt, metal iron salt, metal nickel salt, metal copper salt or metal magnesium salt or any one of hydrates thereof.
3. The method for preparing the polyolefin-based lithium ion battery composite separator according to claim 1, wherein in the step 2), the polyolefin-based film includes but is not limited to: any one of a single-layer polyethylene diaphragm, a single-layer polypropylene diaphragm and a multi-layer composite film of polyethylene and polypropylene.
4. The method for preparing the composite separator of the polyolefin-based lithium ion battery according to claim 3, wherein the multi-layer composite film of polyethylene and polypropylene includes but is not limited to: polypropylene and polyethylene double-layer film, polypropylene and polypropylene double-layer film and polypropylene, polyethylene and polypropylene three-layer composite film.
5. The method for preparing the polyolefin-based lithium ion battery composite separator according to claim 1, wherein in the step 1), the KMnO is added 4 The concentration of the solution is 0.1M to the saturation concentration; the ratio of the amount of the transition metal salt to the amount of the potassium permanganate is 1 (1-30).
6. The preparation method of the polyolefin-based lithium ion battery composite membrane according to claim 1, wherein the reaction time is 30min to 7d, the reaction temperature is 25 to 60 ℃, and the reaction mode is standing or ultrasonic.
7. A composite separator produced by the production method according to any one of claims 1 to 6.
8. Use of a composite membrane according to claim 7, wherein: the method is used for preparing lithium-sulfur batteries, lithium batteries, supercapacitors or in the field of photocatalysis.
9. Use of a composite membrane according to claim 7, wherein: as a lithium sulfur battery separator.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116315463A (en) * | 2023-05-11 | 2023-06-23 | 中创新航科技集团股份有限公司 | Lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116315463A (en) * | 2023-05-11 | 2023-06-23 | 中创新航科技集团股份有限公司 | Lithium battery |
| CN116315463B (en) * | 2023-05-11 | 2023-08-18 | 中创新航科技集团股份有限公司 | Lithium battery |
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