CN111599966A - Lithium battery diaphragm material and preparation method and application thereof - Google Patents
Lithium battery diaphragm material and preparation method and application thereof Download PDFInfo
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- CN111599966A CN111599966A CN202010474547.0A CN202010474547A CN111599966A CN 111599966 A CN111599966 A CN 111599966A CN 202010474547 A CN202010474547 A CN 202010474547A CN 111599966 A CN111599966 A CN 111599966A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- 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
Abstract
The invention provides a lithium battery diaphragm material which is prepared from the following raw materials: graphene oxide, ultra-high molecular weight polyethylene, silver nitrate, tetraethyl titanate, citric acid and o-dichlorobenzene. Compared with the conventional diaphragm, the diaphragm material obtained by the invention has excellent wettability, high porosity and good air permeability, can obviously improve the electrochemical performance of the battery, and is simple and convenient in process, high in yield and easy for commercial production; the invention can prevent polysulfide from passing through the diaphragm under the condition of ensuring lithium ion conductivity, slows down shuttle effect, provides a diaphragm with ion selectivity, obviously improves the electrochemical performance of the lithium-sulfur battery, has small discharge capacity attenuation in the circulating process and obviously improves the circulating stability, and can be applied to the diaphragm material of the quick-charging lithium battery.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a lithium battery diaphragm material and a preparation method and application thereof.
Background
Lithium electrochemical cells, more commonly referred to as batteries (packs), are widely used in a variety of military and commercial products. Many of these products use high energy and high power batteries. Due in part to the miniaturization of portable electronic devices, it is desirable to develop smaller lithium batteries with increased power capacity and service life. The lithium ion battery mainly comprises four materials, namely a positive electrode material, a negative electrode material, electrolyte and a diaphragm. The diaphragm is a microporous film arranged between the anode and the cathode of the battery, so that lithium ions can freely pass through the diaphragm, and the direct contact of the anode and the cathode is blocked to prevent short circuit.
The battery diaphragm is one of the key materials of the lithium battery, and mainly plays a role in preventing the contact of the positive electrode and the negative electrode, so that the short circuit caused by the contact of the positive electrode and the negative electrode is prevented, and electrolyte ions can freely migrate and pass through the battery diaphragm. Therefore, the separator has a decisive influence on the battery capacity, cycle performance, charge/discharge current density, safety and other characteristic parameters. It can be said that the separator having excellent electrochemical properties plays an important role in improving the overall performance of the battery. In addition, the intermediate product lithium polysulfide is highly soluble in the organic electrolyte, reacts with lithium to form a final discharge product, and is deposited on the surface of the negative electrode, so that a shuttle effect is caused, and the performance of the battery is reduced. Since the formation of lithium polysulfide is unavoidable, the lithium polysulfide is suppressed as much as possible on one side of the separator, and migration thereof to the negative electrode is suppressed, whereby the overall performance of the battery can be improved. At present, the lithium battery diaphragm used in the market is mainly a polyolefin diaphragm with a microporous structure, and comprises a single-layer polyethylene, a single-layer polypropylene and a polyolefin three-layer composite film. Although the traditional polyolefin microporous diaphragm has good chemical stability, thin thickness and high mechanical property, in order to improve the high-rate charge and discharge performance and safety performance of the power lithium battery, a novel high-performance lithium battery diaphragm is urgently needed to be developed. There is an increasing interest in improving the safety of lithium battery separators by improving their performance.
Disclosure of Invention
Compared with the conventional diaphragm, the lithium battery diaphragm material has excellent wettability, high porosity and good air permeability, can obviously improve the electrochemical performance of a battery, and is simple and convenient in process, high in yield and easy for commercial production; the invention can prevent polysulfide from passing through the diaphragm under the condition of ensuring lithium ion conductivity, slows down shuttle effect, provides a diaphragm with ion selectivity, obviously improves the electrochemical performance of the lithium-sulfur battery, has small discharge capacity attenuation in the circulating process and obviously improves the circulating stability, and can be applied to the diaphragm material of the quick-charging lithium battery.
The technical scheme of the invention is realized as follows:
the invention provides a lithium battery diaphragm material which is prepared from the following raw materials: graphene oxide, ultra-high molecular weight polyethylene, silver nitrate, tetraethyl titanate, citric acid and o-dichlorobenzene.
The ultrahigh molecular weight polyethylene (UHMWPE) has good anti-friction property, lubricity and impact resistance, the prepared graphene oxide-nano silver titanium/ultrahigh molecular weight polyethylene composite is hydrolyzed by silver nitrate and tetraethyl titanate under the action of citric acid and ammonia water to form nano silver titanium composite powder; the graphene oxide is dispersed in the solution to form a uniform and stable dispersion liquid, the graphene oxide is dispersed in the solution to form a lamellar structure, the powdery ultrahigh molecular weight polyethylene is also a uniform and stable solution under high-temperature high-speed stirring, and in addition, the nano silver titanium compound powder is added. When hot press forming is carried out, certain pressure is applied to the surface of the material, so that the material can be pressed more tightly. In the process of material forming, due to the lamellar structure of the graphene oxide and the powdery structure of the nano silver-titanium compound, the specific surface areas of the graphene oxide and the nano silver-titanium compound are large, the function of a nucleating agent is achieved to a certain extent, more microcrystalline areas are generated around the ultra-high molecular weight polyethylene, nucleation is accelerated, further crystallization of the composite material is accelerated, and finally a uniform phase is formed, so that the graphene oxide-nano silver-titanium/ultra-high molecular weight polyethylene composite is obtained, and meanwhile, the graphene oxide-nano silver-titanium compound has good conductive performance, has excellent wettability, high porosity and good air permeability, and can remarkably improve the electrochemical performance of the battery. (ii) a
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 5-10 parts of graphene oxide, 10-30 parts of ultra-high molecular weight polyethylene, 1-3 parts of silver nitrate, 2-5 parts of tetraethyl titanate, 0.5-3 parts of citric acid and 10-20 parts of o-dichlorobenzene.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 6-9 parts of graphene oxide, 15-25 parts of ultra-high molecular weight polyethylene, 1.5-2.5 parts of silver nitrate, 3-4.5 parts of tetraethyl titanate, 1-2.5 parts of citric acid and 12-18 parts of o-dichlorobenzene.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 7 parts of graphene oxide, 20 parts of ultra-high molecular weight polyethylene, 2 parts of silver nitrate, 4 parts of tetraethyl titanate, 2.2 parts of citric acid and 15 parts of o-dichlorobenzene.
As a further improvement of the invention, the molecular weight of the ultra-high molecular weight polyethylene ranges between 180-300 ten thousand.
The invention further provides a preparation method of the lithium battery diaphragm material, which comprises the following steps:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly dropwise adding ammonia water to adjust the pH value, stirring and reacting at 70-80 ℃ to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain dry gel, transferring the dry gel into a muffle furnace, heating to 450-550 ℃, roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating in an oil bath to a first temperature, heating for 10-30min, adding the o-dichlorobenzene solution of graphene oxide, fully stirring and mixing, raising the temperature to a second temperature, adding the fine powder obtained in the step S1, stirring and reacting for 2-5h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing at a third temperature for 10-20min, and cooling to room temperature to obtain the lithium battery diaphragm material.
As a further improvement of the invention, the mass fraction of the ammonia water in the step S1 is 15-30 wt%, and the pH is adjusted to 9-10.
As a further improvement of the present invention, in the step S2, the mass fraction of graphene oxide in the o-dichlorobenzene solution of graphene oxide is 2-5%.
As a further improvement of the present invention, in step S2, the first temperature is 120-140 ℃, the second temperature is 150-170 ℃, and the third temperature is 180-200 ℃.
The invention further protects the application of the lithium battery diaphragm material in preparing the quick-charging lithium battery diaphragm.
The invention has the following beneficial effects: the ultrahigh molecular weight polyethylene has good anti-friction property, lubricity and impact resistance, graphene oxide with good conductivity is compounded with the ultrahigh molecular weight polyethylene, and meanwhile, the graphene oxide-nano silver titanium/ultrahigh molecular weight polyethylene compound prepared by a sol-gel method is combined, so that the atomic-scale uniform mixing and low synthesis temperature of reactants can be realized, and the prepared product has small (mostly nano) particle size, good uniformity, large specific surface area and easily controlled form and composition;
compared with the conventional diaphragm, the diaphragm material obtained by the invention has excellent wettability, high porosity and good air permeability, can obviously improve the electrochemical performance of the battery, and is simple and convenient in process, high in yield and easy for commercial production; the invention can prevent polysulfide from passing through the diaphragm under the condition of ensuring lithium ion conductivity, slows down shuttle effect, provides a diaphragm with ion selectivity, obviously improves the electrochemical performance of the lithium-sulfur battery, has small discharge capacity attenuation in the circulating process and obviously improves the circulating stability, and can be applied to the diaphragm material of the quick-charging lithium battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The ultra-high molecular weight polyethylene (UHMWPE) is unbranched linear polyethylene with the molecular weight of more than 150 ten thousand, and the molecular weight of the invention is preferably 150-800 ten thousand. In the embodiment, the ultrahigh molecular weight polyethylene is selected from the UHMWPE 4130 with the molecular weight of 680 ten thousand.
Copper ferrite, reference of preparation method: hydrothermal synthesis of CuFe2O4Lithium battery anode material and performance study [ J]Journal of Hubei second academy of academic Hubei 2015, 32 (8): 1-4.
The preparation method of the graphene oxide comprises the following steps:
step one, weighing 10G of natural graphite powder (G), 4G of potassium persulfate and 10G of phosphorus pentoxide, adding the natural graphite powder (G), the potassium persulfate and the phosphorus pentoxide into a three-neck flask filled with 24mL of sulfuric acid under the condition of stirring, firstly reacting for 3h in a constant-temperature water bath at 60 ℃, then moving the three-neck flask into a constant-temperature water bath at 25 ℃ for reacting for 5h, performing suction filtration, washing the three-neck flask to be neutral by using ionized water, and drying the three-neck flask in the air to obtain pre-oxidized graphite (P-G);
step two, weighing l g pre-oxidized graphite, adding the pre-oxidized graphite into a three-neck flask filled with 25mL sulfuric acid under the condition of stirring, putting the three-neck flask into an ice-water bath, adding 3g potassium permanganate after the pre-oxidized graphite is completely dissolved, reacting for 2 hours, moving the three-neck flask into a constant-temperature water bath at 35 ℃ for reacting for 40min, finally adding deionized water, continuing to react for 1 hour at 35 ℃, and finally dropwise adding 30% of H2O2So that the solution turned bright yellow until no more gas was formed. The mixture was filtered by centrifugation while hot and washed to neutrality with a large amount of 5% hydrochloric acid and deionized water. And (3) carrying out ultrasonic oscillation on the final precipitate by l h, pouring the final precipitate into a culture dish, and drying for 24 hours at 90 ℃ to obtain Graphite Oxide (GO).
Tetraethoxytitanate, CAS No.: 3087-36-3.
Silver nitrate, CAS number: 7761-88-8.
Citric acid, CAS No.: 77-92-9.
O-dichlorobenzene, CAS No.: 95-50-1. All chemicals were purchased from the national pharmaceutical group.
Example 1
The raw materials comprise the following components in parts by weight: 5 parts of graphene oxide, 10 parts of ultra-high molecular weight polyethylene, 1 part of silver nitrate, 2 parts of tetraethyl titanate, 0.5 part of citric acid and 10 parts of o-dichlorobenzene.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly dropwise adding 15 wt% of ammonia water to adjust the pH value to 9, stirring and reacting at 70 ℃ to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain xerogel, transferring the xerogel into a muffle furnace, heating to 450 ℃ for roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution in an oil bath to 120 ℃, heating the solution for 10min, adding an o-dichlorobenzene solution of graphene oxide (the mass fraction of the graphene oxide is 2%), fully stirring and mixing the solution, raising the temperature to 150 ℃, adding the fine powder obtained in the step S1, stirring and reacting for 2h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture for 10min at 180 ℃, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Example 2
The raw materials comprise the following components in parts by weight: 10 parts of graphene oxide, 30 parts of ultra-high molecular weight polyethylene, 3 parts of silver nitrate, 5 parts of tetraethyl titanate, 3 parts of citric acid and 20 parts of o-dichlorobenzene.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly dropwise adding 30 wt% of ammonia water to adjust the pH value to 10, stirring and reacting at 80 ℃ to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain xerogel, transferring the xerogel into a muffle furnace, heating to 550 ℃, roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution to 140 ℃ in an oil bath, heating the solution for 30min, adding an o-dichlorobenzene solution of graphene oxide (the mass fraction of the graphene oxide is 5%), fully stirring and mixing the solution, raising the temperature to 170 ℃, adding the fine powder obtained in the step S1, stirring and reacting for 5h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture for 20min at 200 ℃, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Example 3
The raw materials comprise the following components in parts by weight: 6 parts of graphene oxide, 15 parts of ultra-high molecular weight polyethylene, 1.5 parts of silver nitrate, 3 parts of tetraethyl titanate, 1 part of citric acid and 12 parts of o-dichlorobenzene.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly dropwise adding 17 wt% of ammonia water to adjust the pH value to 9.2, stirring and reacting at 72 ℃ to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain xerogel, transferring the xerogel into a muffle furnace, heating to 470 ℃ for roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution to 125 ℃ in an oil bath, heating the solution for 15min, adding an o-dichlorobenzene solution of graphene oxide (the mass fraction of the graphene oxide is 2.5%), fully stirring and mixing the solution, raising the temperature to 155 ℃, adding the fine powder obtained in the step S1, stirring and reacting the mixture for 3h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture for 12min at 185 ℃, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Example 4
The raw materials comprise the following components in parts by weight: 9 parts of graphene oxide, 25 parts of ultra-high molecular weight polyethylene, 2.5 parts of silver nitrate, 4.5 parts of tetraethyl titanate, 2.5 parts of citric acid and 18 parts of o-dichlorobenzene.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly adding 27 wt% of ammonia water dropwise to adjust the pH value to 9.8, stirring the solution at 78 ℃ to react to form hydrogel, transferring the hydrogel into an oven, heating the hydrogel to dryness to obtain xerogel, transferring the xerogel into a muffle furnace, heating the xerogel to 520 ℃, roasting the xerogel, cooling the xerogel, and grinding the;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution in an oil bath to 135 ℃, heating the solution for 25min, adding an o-dichlorobenzene solution of graphene oxide (the mass fraction of the graphene oxide is 4.5%), fully stirring and mixing the solution, raising the temperature to 165 ℃, adding the fine powder obtained in the step S1, stirring and reacting for 4h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture at 195 ℃ for 18min, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Example 5
The raw materials comprise the following components in parts by weight: 7 parts of graphene oxide, 20 parts of ultra-high molecular weight polyethylene, 2 parts of silver nitrate, 4 parts of tetraethyl titanate, 2.2 parts of citric acid and 15 parts of o-dichlorobenzene.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly dropwise adding 22 wt% of ammonia water to adjust the pH value to 9.5, stirring and reacting at 75 ℃ to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain xerogel, transferring the xerogel into a muffle furnace, heating to 500 ℃ for roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution to 130 ℃ in an oil bath, heating the solution for 20min, adding an o-dichlorobenzene solution of graphene oxide (the mass fraction of the graphene oxide is 3.5%), fully stirring and mixing the solution, raising the temperature to 160 ℃, adding the fine powder obtained in the step S1, stirring and reacting the mixture for 3h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture for 15min at 190 ℃, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Example 6:
the raw materials comprise the following components in parts by weight: 7 parts of graphene oxide, 20 parts of ultra-high molecular weight polyethylene, 2 parts of silver nitrate, 4 parts of tetraethyl titanate, 2.2 parts of citric acid, 15 parts of o-dichlorobenzene and 2 parts of copper ferrite.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly dropwise adding 22 wt% of ammonia water to adjust the pH value to 9.5, stirring and reacting at 75 ℃ to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain xerogel, transferring the xerogel into a muffle furnace, heating to 500 ℃ for roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution to 130 ℃ in an oil bath, heating the solution for 20min, adding the o-dichlorobenzene solution of graphene oxide (the mass fraction of the graphene oxide is 3.5%), fully stirring and mixing the solution, raising the temperature to 160 ℃, adding the fine powder obtained in the step S1 and copper ferrite, stirring the mixture for reaction for 3h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture for 15min at 190 ℃, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Copper ferrite, reference to preparation method: gorgeous, shogawa hydrothermal synthesis of CuFe2O4 lithium battery anode material and performance study [ J ] proceedings of the second academy of teaching north and Hubei, 2015, 32 (8): 1-4.
Comparative example 1
Compared to example 5, no silver nitrate was added, and the other conditions were unchanged.
The raw materials comprise the following components in parts by weight: 7 parts of graphene oxide, 20 parts of ultra-high molecular weight polyethylene, 6 parts of tetraethyl titanate, 2.2 parts of citric acid and 15 parts of o-dichlorobenzene.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing tetraethyl titanate and citric acid, dissolving in deionized water, stirring until the tetraethyl titanate and the citric acid are dissolved, slowly adding 22 wt% ammonia water dropwise to adjust the pH value to 9.5, stirring at 75 ℃ to react to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain xerogel, transferring the xerogel into a muffle furnace, heating to 500 ℃ for roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution to 130 ℃ in an oil bath, heating the solution for 20min, adding an o-dichlorobenzene solution of graphene oxide (the mass fraction of the graphene oxide is 3.5%), fully stirring and mixing the solution, raising the temperature to 160 ℃, adding the fine powder obtained in the step S1, stirring and reacting the mixture for 3h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture for 15min at 190 ℃, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Comparative example 2
In comparison with example 5, no tetraethyl titanate was added, and the other conditions were unchanged.
The raw materials comprise the following components in parts by weight: 7 parts of graphene oxide, 20 parts of ultra-high molecular weight polyethylene, 6 parts of silver nitrate, 2.2 parts of citric acid and 15 parts of o-dichlorobenzene.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing silver nitrate and citric acid, dissolving the silver nitrate and the citric acid in deionized water, stirring until the silver nitrate and the citric acid are dissolved, slowly dropwise adding 22 wt% of ammonia water to adjust the pH value to 9.5, stirring and reacting at 75 ℃ to change the solution into a silver-ammonia solution, transferring the silver-ammonia solution into a drying oven, heating and evaporating to dryness to obtain dry powder, transferring the dry powder into a muffle furnace, heating to 500 ℃ for roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution to 130 ℃ in an oil bath, heating the solution for 20min, adding an o-dichlorobenzene solution of graphene oxide (the mass fraction of the graphene oxide is 3.5%), fully stirring and mixing the solution, raising the temperature to 160 ℃, adding the fine powder obtained in the step S1, stirring and reacting the mixture for 3h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture for 15min at 190 ℃, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Comparative example 3
Compared with example 5, no graphene oxide was added, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 20 parts of ultra-high molecular weight polyethylene, 2 parts of silver nitrate, 4 parts of tetraethyl titanate, 2.2 parts of citric acid and 15 parts of o-dichlorobenzene.
The preparation method of the lithium battery diaphragm material comprises the following steps:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly dropwise adding 22 wt% of ammonia water to adjust the pH value to 9.5, stirring and reacting at 75 ℃ to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain xerogel, transferring the xerogel into a muffle furnace, heating to 500 ℃ for roasting, cooling and grinding into fine powder;
s2, placing the ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating the solution to 130 ℃ in an oil bath, heating the solution for 20min, fully stirring and mixing the solution, raising the temperature to 160 ℃, adding the fine powder obtained in the step S1, stirring and reacting the mixture for 3h, carrying out suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing the mixture for 15min at 190 ℃, and cooling the mixture to room temperature to obtain the lithium battery diaphragm material.
Test example 1 Performance test
The battery separator materials prepared in examples 1 to 5 and comparative examples 1 to 3 of the present invention and commercially available battery separator materials (purchased from shanghai jee new materials science and technology) were subjected to performance tests, and the structures thereof are shown in table 1.
TABLE 1
As can be seen from Table 1 above, the separator material prepared by the present invention has more excellent performance, which is obviously superior to that of comparative examples 1-3 and commercially available separator materials.
In example 6, copper ferrite was added, so that the separator material of the present invention had better performance. The copper ferrite is used as a blending substance of a diaphragm material of a lithium ion battery, has large surface tension, organic solvent molecules are difficult to embed into electrode lattices, the damage of the embedding of the solvent molecules to the diaphragm structure can be well prevented, sub-band gaps are possibly generated by surface defects, the service life of the diaphragm material is favorably prolonged, the conductivity is improved, and the air permeability is increased.
In the comparative examples 1 and 2, silver nitrate or tetraethyl titanate is not added respectively, so that the conductivity is remarkably reduced, and other properties are slightly reduced, so that the addition of the silver nitrate or tetraethyl titanate has a remarkable promoting effect on the conductivity of the separator material and a synergistic effect.
Compared with a single nano silver compound or a single nano titanium compound, the nano silver-titanium composite prepared by hydrolyzing the silver nitrate and the tetraethyl titanate has better conductivity and photocatalysis performance, the electrochemical performance of the battery is obviously improved, and a diaphragm prepared by compounding the nano silver-titanium composite with the ultra-high molecular weight polyethylene prevents polysulfide from passing through the diaphragm under the condition of ensuring the lithium ion conductivity, so that the shuttle effect is reduced.
Compared with the prior art, the graphene oxide is not added in the comparative example 3, the mechanical property and the conductivity of the prepared diaphragm material are obviously reduced, and the performance of the diaphragm material can be obviously improved by adding the graphene oxide.
Test example 2
The battery separator materials prepared in examples 1 to 5 and comparative examples 1 to 3 of the present invention and a commercially available battery separator material (available from shanghai jejie new materials science) were prepared into lithium batteries, charged at room temperature (25 ℃) and a constant current of about 0.5C rate until a voltage reached 4.20V, charged at a constant voltage of 4.20V until a current reached 0.05C, and then discharged at a constant current of 0.5C rate until a voltage reached 2.75V.
During the second cycle, the lithium battery was charged at a constant current of about 0.5C rate until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, and then discharged at a constant current of 0.2C rate until the voltage reached 2.80V.
During the third cycle, the lithium battery was charged at a constant current of about 0.5C rate until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, and then discharged at a constant current of 0.2C rate until the voltage reached 2.80V. The discharge capacity in the third cycle was regarded as a standard capacity.
During the fourth cycle, the lithium cell was charged at a rate of about 0.5C until the voltage reached 4.20V, charged at a constant voltage of 4.20V until the current reached 0.05C, stored in an oven at 60 ℃ for 60 days, and then the cell was removed and subjected to a fourth discharge cycle at a rate of 0.1C until the voltage reached 2.75V. Some charge and discharge results are shown in table 2 below. The capacity retention rate after high-temperature storage can be defined as follows.
Capacity retention after high-temperature storage [% ] is [ discharge capacity/standard capacity after high-temperature exposure in the fourth cycle ] × 100%.
(Standard Capacity is discharge Capacity in third cycle)
TABLE 2
As shown in table 2 above, lithium batteries prepared including the separator materials of examples 1-5 of the present invention showed significantly increased stability at high temperatures, as compared to lithium batteries manufactured in comparative examples 1-3 and commercially available separator materials.
In example 6, copper ferrite was added, so that the separator material of the present invention had better performance. The copper ferrite powder with the micro-nano structure has large specific surface area, an anisotropic interface accounts for 7% of the material, the interface reaction position is increased, and the polarization phenomenon in the electrochemical process of the electrode is favorably reduced.
Compared with the prior art, the ultrahigh molecular weight polyethylene has good anti-friction property, lubricity and impact resistance, graphene oxide with good conductivity is compounded with the ultrahigh molecular weight polyethylene, and meanwhile, the graphene oxide-nano silver titanium/ultrahigh molecular weight polyethylene compound prepared by the sol-gel method is combined, so that the atomic-level uniform mixing and low synthesis temperature of reactants can be realized, and the prepared product has small particle size (mostly nano-scale), good uniformity, large specific surface area and easily controlled form and composition;
compared with the conventional diaphragm, the diaphragm material obtained by the invention has excellent wettability, high porosity and good air permeability, can obviously improve the electrochemical performance of the battery, and is simple and convenient in process, high in yield and easy for commercial production; the invention can prevent polysulfide from passing through the diaphragm under the condition of ensuring lithium ion conductivity, slows down shuttle effect, provides a diaphragm with ion selectivity, obviously improves the electrochemical performance of the lithium-sulfur battery, has small discharge capacity attenuation in the circulating process and obviously improves the circulating stability, and can be applied to the diaphragm material of the quick-charging lithium battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The lithium battery diaphragm material is characterized by being prepared from the following raw materials: graphene oxide, ultra-high molecular weight polyethylene, silver nitrate, tetraethyl titanate, citric acid and o-dichlorobenzene.
2. The lithium battery diaphragm material as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 5-10 parts of graphene oxide, 10-30 parts of ultra-high molecular weight polyethylene, 1-3 parts of silver nitrate, 2-5 parts of tetraethyl titanate, 0.5-3 parts of citric acid and 10-20 parts of o-dichlorobenzene.
3. The lithium battery diaphragm material as claimed in claim 2, which is prepared from the following raw materials in parts by weight: 6-9 parts of graphene oxide, 15-25 parts of ultra-high molecular weight polyethylene, 1.5-2.5 parts of silver nitrate, 3-4.5 parts of tetraethyl titanate, 1-2.5 parts of citric acid and 12-18 parts of o-dichlorobenzene.
4. The lithium battery diaphragm material as claimed in claim 3, which is prepared from the following raw materials in parts by weight: 7 parts of graphene oxide, 20 parts of ultra-high molecular weight polyethylene, 2 parts of silver nitrate, 4 parts of tetraethyl titanate, 2.2 parts of citric acid and 15 parts of o-dichlorobenzene.
5. The lithium battery separator material as claimed in claim 1, wherein the molecular weight of the ultra-high molecular weight polyethylene is in the range of 180-300 ten thousand.
6. A method for preparing a lithium battery separator material as claimed in any one of claims 1 to 4, comprising the steps of:
s1, weighing tetraethyl titanate, silver nitrate and citric acid, dissolving the tetraethyl titanate, the silver nitrate and the citric acid in deionized water, stirring until the tetraethyl titanate, the silver nitrate and the citric acid are dissolved, slowly dropwise adding ammonia water to adjust the pH value, stirring and reacting at 70-80 ℃ to change the solution into hydrogel, transferring the hydrogel into an oven, heating and evaporating to dryness to obtain dry gel, transferring the dry gel into a muffle furnace, heating to 450-550 ℃, roasting, cooling and grinding into fine powder;
s2, placing ultra-high molecular weight polyethylene into an o-dichlorobenzene solution, heating in an oil bath to a first temperature, heating for 10-30min, adding the o-dichlorobenzene solution of graphene oxide, fully stirring and mixing, raising the temperature to a second temperature, adding the fine powder obtained in the step S1, stirring and reacting for 2-5h, performing suction filtration on the uniformly dispersed mixed solution, drying solid filter residues to constant weight, pressurizing at a third temperature for 10-20min, and cooling to room temperature to obtain the lithium battery diaphragm material.
7. The method according to claim 6, wherein the ammonia water in step S1 has a mass fraction of 15 to 30 wt%, and the pH is adjusted to 9 to 10.
8. The method according to claim 6, wherein the mass fraction of graphene oxide in the o-dichlorobenzene solution of graphene oxide in step S2 is 2-5%.
9. The method as claimed in claim 6, wherein the first temperature in step S2 is 140 ℃, the second temperature is 150-170 ℃, and the third temperature is 180-200 ℃.
10. Use of a lithium battery separator material as claimed in any one of claims 1 to 5 for the preparation of a separator for a fast-charging lithium battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112635908A (en) * | 2020-12-31 | 2021-04-09 | 界首市天鸿新材料股份有限公司 | Preparation method of modified polyethylene lithium battery diaphragm |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102743977A (en) * | 2012-06-18 | 2012-10-24 | 上海百菲特环保科技有限公司 | Preparation method of novel ultrahigh molecular weight polyethylene hollow fiber membrane |
| CN104425809A (en) * | 2013-08-28 | 2015-03-18 | 奇瑞汽车股份有限公司 | Lithium ion battery positive electrode material, preparation method of lithium ion battery positive electrode material, lithium ion battery comprising lithium ion battery positive electrode material |
| CN104716382A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Lithium-sulfur battery structure |
| CN105576212A (en) * | 2016-02-19 | 2016-05-11 | 东莞市迈科科技有限公司 | Method for preparing titanium dioxide nanosheet coated graphene anode material of lithium ion battery |
| CN106859658A (en) * | 2017-02-14 | 2017-06-20 | 西南政法大学 | The preparation of spinel-type Preen nono powder and its finger mark process for show |
| CN107446221A (en) * | 2017-09-27 | 2017-12-08 | 中玺新材料（安徽）有限公司 | A kind of ultra-high molecular weight polyethylene/graphite alkene composite |
| CN108435183A (en) * | 2018-03-17 | 2018-08-24 | 启东祥瑞建设有限公司 | A kind of spinel-type AFe2O4The preparation method of catalyst |
| CN109244340A (en) * | 2018-09-12 | 2019-01-18 | 肇庆市华师大光电产业研究院 | A kind of lithium-sulfur cell functionality diaphragm coating material and preparation method thereof |
-
2020
- 2020-05-29 CN CN202010474547.0A patent/CN111599966A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102743977A (en) * | 2012-06-18 | 2012-10-24 | 上海百菲特环保科技有限公司 | Preparation method of novel ultrahigh molecular weight polyethylene hollow fiber membrane |
| CN104425809A (en) * | 2013-08-28 | 2015-03-18 | 奇瑞汽车股份有限公司 | Lithium ion battery positive electrode material, preparation method of lithium ion battery positive electrode material, lithium ion battery comprising lithium ion battery positive electrode material |
| CN104716382A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Lithium-sulfur battery structure |
| CN105576212A (en) * | 2016-02-19 | 2016-05-11 | 东莞市迈科科技有限公司 | Method for preparing titanium dioxide nanosheet coated graphene anode material of lithium ion battery |
| CN106859658A (en) * | 2017-02-14 | 2017-06-20 | 西南政法大学 | The preparation of spinel-type Preen nono powder and its finger mark process for show |
| CN107446221A (en) * | 2017-09-27 | 2017-12-08 | 中玺新材料（安徽）有限公司 | A kind of ultra-high molecular weight polyethylene/graphite alkene composite |
| CN108435183A (en) * | 2018-03-17 | 2018-08-24 | 启东祥瑞建设有限公司 | A kind of spinel-type AFe2O4The preparation method of catalyst |
| CN109244340A (en) * | 2018-09-12 | 2019-01-18 | 肇庆市华师大光电产业研究院 | A kind of lithium-sulfur cell functionality diaphragm coating material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112635908A (en) * | 2020-12-31 | 2021-04-09 | 界首市天鸿新材料股份有限公司 | Preparation method of modified polyethylene lithium battery diaphragm |
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