CN115414909B - Lithium ion battery electrolyte solvent water removing agent and preparation method and application thereof - Google Patents

Lithium ion battery electrolyte solvent water removing agent and preparation method and application thereof Download PDF

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CN115414909B
CN115414909B CN202210910853.3A CN202210910853A CN115414909B CN 115414909 B CN115414909 B CN 115414909B CN 202210910853 A CN202210910853 A CN 202210910853A CN 115414909 B CN115414909 B CN 115414909B
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molecular sieve
water
strips
mixture
solvent
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CN115414909A (en
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杨建建
陈世安
谭礼林
梁智敏
莫世广
刘志锐
丁湘浓
于争飞
王熙
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Guangdong Laboratory Of Chemistry And Fine Chemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3028—Granulating, agglomerating or aggregating
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a water remover for lithium ion battery electrolyte and a preparation method and application thereof, and belongs to the technical field of lithium ion battery electrolyte.

Description

Lithium ion battery electrolyte solvent water removing agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery electrolyte production, and particularly relates to a method for preparing a lithium ion battery electrolyte solvent water scavenger, and also relates to the lithium ion battery electrolyte solvent water scavenger prepared by the method, and also relates to application of the water scavenger.
Background
The lithium ion battery is a secondary battery which is formed by respectively using two compounds capable of reversibly intercalating and deintercalating lithium ions as positive and negative electrodes, wherein during charging, lithium ions are deintercalated from a positive electrode, are intercalated into a negative electrode through an electrolyte, and the negative electrode is in a lithium-rich state, and during discharging, the negative electrode is opposite, so that people can visually refer to the lithium ion battery as a rocking chair type battery by a unique mechanism that the charge and discharge of the battery are completed by transferring lithium ions between the positive electrode and the negative electrode. Since the development of lithium ion batteries in the 70 th century, as the population increases and the global resources are limited, research and development of lithium ion batteries having the advantages of light weight, large capacity, no memory effect, no toxic substances and the like are being carried out, the development of lithium ion batteries is today, the application fields of lithium ion batteries are developed from the original mobile phones and notebooks to Bluetooth headsets, digital products, electric tools, electric bicycles, electric automobiles, aviation tools, solar energy, military industry fields and the like, and the application range of lithium ion batteries is further expanded and spread to various fields in life as research is continued.
The electrolyte is called as the 'blood' of the battery, is an important component of the lithium ion battery, and plays a role in conducting an ion conductor between the anode and the cathode of the battery, and the performance of the battery is directly influenced by the performance of the battery. The lithium ion battery electrolyte mainly comprises lithium salt, an organic solvent and various functional additives, and has important influence on various performances of the lithium ion battery, such as capacity, internal resistance, circulation, multiplying power, safety and the like. The electrolyte is generally formed by a cyclic carbonate solvent such as Ethylene Carbonate (EC), propylene Carbonate (PC) and a chain carbonate solvent such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC) and the like, and has the characteristics of good electrochemical stability, high dielectric constant, low melting point, high flash point, safety, no toxicity and the like.
Electrolyte solute lithium salt LiPF 6 Because of high solubility in carbonate solvents, high conductivity and good stability to graphite negative electrodes, the lithium salt is the main lithium salt used in the current commercial electrolyte, however LiPF 6 Poor thermal stability and sensitivity to moisture, and is in trace amountsWater can be decomposed to generate PF 5 HF, liF, etc., thereby corroding the current collector, the SEI film, and the electrode active material, so that the battery performance is rapidly attenuated, and the cycle performance is poor. In addition, along with the improvement requirement of specific energy density of the lithium ion battery, the ternary positive electrode material with low cost, high voltage and high gram capacity, such as nickel cobalt lithium manganate, nickel cobalt lithium aluminate and the like, is widely applied to the lithium ion battery, especially the power lithium ion battery, and is considered as the main current positive electrode material of the next generation lithium ion battery, but the ternary positive electrode material has strong water absorption, especially under the high voltage and higher nickel content, the decomposition process of the solute lithium salt of the conventional electrolyte is greatly accelerated, and the battery is seriously inflated and has poor cycle performance. Therefore, the moisture content of the electrolyte must be strictly controlled during the production and use processes, so that the purity of the product can be ensured.
At present, the most commonly used water removal process of the lithium ion battery electrolyte solvent is to introduce an organic solvent into a 4A or 5A molecular sieve for water removal. However, although the molecular sieves can remove moisture in the solvent or other impurities affecting the electrochemical performance of the electrolyte, as the molecular sieves are aluminosilicate and have acid in the structure, the carbonate solvent is decomposed, so that the impurity content in the electrolyte is increased, the purity of the electrolyte is reduced, the impurity adsorption content of the molecular sieves is correspondingly increased along with the prolonged service time, the dewatering efficiency of the molecular sieves is reduced, and the replacement and use frequency of the molecular sieves is increased.
Therefore, the water scavenger which has high water adsorption capacity and does not cause solvolysis of the electrolyte of the lithium ion battery is obtained, and has important practical significance.
Disclosure of Invention
In order to solve the problems that the existing water scavenger for the lithium ion battery electrolyte solvent is easy to cause decomposition of carbonate solvents, and further influences the purity of the electrolyte, the water removal effect of a molecular sieve and the service cycle to be shortened, the invention provides the water scavenger for the lithium ion battery electrolyte solvent after a great deal of research is carried out on the existing lithium ion battery electrolyte.
In a first aspect of the invention, the invention provides a method for preparing a solvent water scavenger for lithium ion battery electrolyte, which comprises the following steps in sequence:
(S1) uniformly mixing a silicon source and a solvent, then adding molecular sieve powder, mixing, vacuumizing the system until the vacuum degree is lower than 80Pa, stirring for 2-18h, drying the system at 80-120 ℃ for 6-18h, and roasting at 550-700 ℃ for 4-8h to obtain a modified molecular sieve;
(S2) uniformly mixing the modified molecular sieve obtained in the step (S1) with a binder, a lubricant and water to obtain a mixture;
(S3) carrying out molding treatment, drying and roasting on the mixture obtained in the step (S2) to obtain the water scavenger for the lithium ion battery electrolyte.
The existing molecular sieve for removing water from the electrolyte solvent is easy to cause decomposition of carbonate solvents due to acidity, so that the impurity content in the electrolyte is increased, the purity of the electrolyte is reduced, and meanwhile, the molecular sieve adsorbs more and more impurities, so that the water removing effect of the molecular sieve is poor, and the service life is shortened. According to the invention, the molecular sieve powder is fully mixed with the modified silicon source and baked at a high temperature, so that silicon oxide is introduced to the surface of the molecular sieve, and under the condition of less influence on the molecular sieve pore structure and the specific surface, the acidity of the molecular sieve is modulated, so that the molecular sieve has higher water removal efficiency, the problem of decomposition of carbonate solvents caused by the molecular sieve can be greatly reduced, the purity of electrolyte can be improved in the using process, and the water remover has better market competitiveness.
Preferably, in the above method, the solvent in the step (S1) is a low boiling point organic solvent, for example, an organic solvent having a boiling point lower than 120 ℃, such as cyclohexane, petroleum ether, carbon tetrachloride, toluene, etc. The silicon source is dissolved in these organic solvents and partial hydrolysis of the silicon source occurs after impregnation of the molecular sieve, whereas unreacted silicon source molecules are vaporized away from the surface of the molecular sieve during drying along with cyclohexane.
Preferably, in the above method, the silicon source in the step (S1) is at least one of methyl orthosilicate, tetraethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, polyphenylmethylsiloxane, and hexamethyl silyl ether.
More preferably, in the above method, the silicon source in the step (S1) is tetraethyl orthosilicate.
On the premise of less influence on the specific surface area and pore structure of the molecular sieve, the decomposition of the carbonic ester solvent can be inhibited by reducing the acid amount on the outer surface of the molecular sieve and reducing the pore size, and the solvent can be decomposed by two modes of acid catalysis and base catalysis, so that the decomposition of carbonic ester under the acid catalysis condition can be inhibited by reducing the acid amount on the outer surface of the molecular sieve; in addition, the size of the pore opening of the molecular sieve is reduced, so that the carbonate solvent can be limited to enter the pore canal of the molecular sieve, the contact with the acid center on the inner surface of the molecular sieve is reduced, and the decomposition of the carbonate in the pore canal of the molecular sieve can be inhibited. The silicon source impregnates the molecular sieve and is baked to form a layer of Si film formed by Si-O-Si units on the outer surface of the molecular sieve, and the Si-O-Si on the Si film penetrates into the pore opening of the molecular sieve to finely adjust the pore opening because the bond length and bond angle of the Si-O-Si are different from those of the Si-O-Al units of the molecular sieve. Although the silicon film has small contribution to the reduction of acid sites, the triethoxy groups formed by partial hydrolysis of the silicon source can react with the hydroxyl groups on the molecular sieve to form new Al-O-Si bonds after roasting, so that the acid sites can be effectively eliminated, and the decomposition of the solvent carbonate solvent for electrolysis can be effectively slowed down by modifying the molecular sieve by the silicon source.
Preferably, in the above method, the molecular sieve powder in the step (S1) is at least one of 4A molecular sieve powder, 3A molecular sieve powder, 5A molecular sieve powder.
Preferably, in the above method, the mass ratio of the solvent to the molecular sieve powder in the step (S1) is (1.5-4): 1. The present invention impregnates the silicon source by an excessive impregnation method, i.e., the solvent is added in an amount greater than the water absorption or pore volume of the molecular sieve itself, and the silicon source with a certain concentration is dissolved in the solvent, so that the loading amount of the silica can also be changed by adjusting the mass ratio of the solvent to the molecular sieve.
Preferably, in the above method, the mass of silica in the silicon source in the step (S1) is 1 to 10% of the mass of the molecular sieve powder, more preferably 2 to 8%.
Preferably, in the above method, when the system is vacuumized in the step (S1), the vacuum degree is below 50Pa, because the air in the molecular sieve pore canal can be vacuumized to form a negative pressure state in the pore canal, and after the silicon source is immersed, the molecular sieve pore canal can make the bonding force between the silicon source molecule and the molecular sieve surface active site stronger under the action of the negative pressure, so as to provide more loading opportunities, and further obtain a more uniform deposition effect.
Preferably, in the above method, the conditions for drying the stirred system in the step (S1) are as follows: the temperature is 100-110 ℃ and the time is 10-18h. The drying temperature in this step needs to be higher than the boiling point of the solvent to remove the solvent as soon as possible.
Preferably, in the above method, the condition for calcining the stirred system in the step (S1) is: under the air atmosphere or the oxygen atmosphere, the temperature is 580-650 ℃ and the time is 5-7h. In the step, the silicon source adsorbed by the molecular sieve is fully decomposed and converted into silicon dioxide, so that the modification of the molecular sieve is realized.
Preferably, in the above method, the parts by weight of the modified molecular sieve, the binder, the lubricant and the water in the step (S2) are:
preferably, in the above method, in the step (S2), the modified molecular sieve obtained in the step (S1) is mixed with a binder, a lubricant and water, firstly, the molecular sieve is mixed with the lubricant uniformly to obtain a mixture, secondly, the binder is mixed with water uniformly to obtain an aqueous binder solution, and finally, the aqueous binder solution is mixed with the mixture uniformly.
Preferably, in the above method, the binder in the step (S2) is a silica sol, and the solid content in the silica sol is 30 to 50%, more preferably 35 to 45%.
The silica sol is used as a binder to play a role in bonding, and the modified molecular sieve powder and the silica sol are mixed, molded, dried and roasted, so that the obtained molecular sieve does not introduce acidic components. In addition, the solid content in the silica sol has a great influence on the viscosity of the silica sol, and the silica sol with too large or too small viscosity is unfavorable for molecular sieve molding.
Preferably, in the above method, the lubricant in the step (S2) is sesbania powder and/or graphite, more preferably sesbania powder.
In the invention, sesbania powder is mainly used as a lubricant, is convenient for molding, and graphite can be used as the lubricant, but is more environment-friendly compared with the sesbania powder, because the sesbania powder is prepared by crushing and sieving endosperm of sesbania seeds of leguminous plants, and the main components are galactose and mannose, the sesbania powder has the characteristics of better water solubility, high viscosity, good gel linkage performance, flocculation, salt tolerance and the like.
Preferably, in the above method, the mass ratio of the modified molecular sieve to the lubricant in the step (S2) is (15-25): 1. If the lubricant is insufficient, the lubrication effect is insufficient, and the demolding effect is affected, so that the water remover is easy to collapse after molding; and if the lubricant amount is too much, the demolding is too fast due to too high lubrication degree, so that the mechanical strength of the water removing agent is insufficient, in addition, the proportion of the lubricant is too high, the proportion of the molecular sieve in the water removing agent can be reduced, the water absorption rate of the formed water removing agent is influenced, the use amount of the water removing agent can be increased, and the water removing cost is further improved.
Preferably, in the above method, the water in the step (S2) is deionized water to avoid introducing unnecessary impurities into the molecular sieve.
Preferably, in the above method, the forming treatment in the step (S3) includes extrusion molding, tabletting molding, ball molding or spray granulation molding. The water scavenger can be filled into the adsorption tower or the adsorption column only after molding, so that the electrolyte solvent can flow through the gaps of particles, if the water scavenger is in a powder form, the fluidity of the electrolyte solvent can be poor and the blockage can be easily caused, and in addition, the powdery water scavenger can also remain in the electrolyte solvent to pollute the electrolyte solvent, so that molding treatment is needed to ensure that the form of the final water scavenger is non-powdery.
Preferably, in the above method, the drying condition in the step (S3) is: the temperature is 100-110 ℃ and the time is 8-16h to remove the water.
Preferably, in the above method, the conditions for performing the calcination in the step (S3) are: the temperature is 550-650 deg.c, more preferably, the time is 4-10h under air atmosphere or oxygen atmosphere.
The preparation method adopts a two-time roasting process, wherein the first roasting is to fully decompose a silicon source to form silicon oxide to be loaded on the surface of the molecular sieve so as to achieve the aim of modifying the molecular sieve, the second roasting is to remove the lubricant so as to avoid influencing the performance of the molecular sieve, in addition, the roasting to remove the lubricant can also play a role of pore forming, a certain amount of pore channels can be formed in the formed water remover after the lubricant is removed by roasting, and the diffusion of electrolyte solvent in water removal is facilitated. In addition, the formed molecular sieve has certain structural strength by the roasting.
The modified molecular sieve is used as a core component of the water scavenger, the binder and the lubricant are added, and the water scavenger is obtained after roasting, so that the preparation process is simple and easy to implement, and the popularization and the use are facilitated.
According to a second aspect of the present invention, there is also provided a water scavenger prepared by the above method.
According to a third aspect of the present invention there is also provided the use of a water scavenger prepared by the above method wherein the use is for the removal of water from a lithium ion battery electrolyte solvent.
The water scavenger disclosed by the invention has higher water removal efficiency, can greatly reduce the problem of decomposition of carbonate solvents caused by the existing water scavenger, can inhibit decomposition of electrolyte solvents while adsorbing water, and further can greatly improve the product performance of the electrolyte. As the service time is prolonged, compared with an unmodified molecular sieve, the method can effectively inhibit the decomposition of the solvent in the process of removing the solvent of the electrolyte, and the content of impurities adsorbed by the water remover is correspondingly reduced, so that the time for reducing the water removing efficiency caused by the adsorption of the impurities by the water remover is correspondingly prolonged, the replacement and use frequency of the molecular sieve water remover is reduced, and the use and maintenance cost of the molecular sieve water remover is saved.
Compared with the prior art, the invention realizes the modulation of the acid property, pore structure parameter and the like of the molecular sieve by modifying the molecular sieve, and the modified molecular sieve is used as the core component of the water scavenger, so that the obtained water scavenger has higher water removal efficiency, can greatly reduce the problem of decomposition of carbonate solvents caused by the existing molecular sieve water scavenger, can improve the purity of the electrolyte solvent while adsorbing water, and can greatly improve the product performance of the electrolyte. In addition, as the service time of the water scavenger is prolonged, compared with an unmodified molecular sieve, the prepared water scavenger can effectively inhibit solvolysis in the process of removing the electrolyte solvent, and impurities which are introduced and adsorbed due to solvolysis of the carbonate can be correspondingly reduced, so that the time of occurrence of the problem of reduced water removal efficiency caused by adsorption of impurities by the molecular sieve can be correspondingly prolonged, and the replacement and use frequency of the molecular sieve can be reduced.
Drawings
FIG. 1 is a diagram showing N of a water scavenger prepared in example 1 of the present invention 2 Adsorption isotherm plot;
FIG. 2 is a NH3-TPD chart of the water scavenger prepared in example 1 of the present invention;
FIG. 3 is a graph showing pore size distribution of the water scavenger prepared in example 1 of the present invention.
Detailed Description
In order to more clearly describe the embodiments of the present invention or technical solutions in the prior art, the technical solutions of the present invention will be described in detail with specific embodiments.
In the following examples, the water used was deionized water to avoid introducing unwanted impurities. Tetraethyl orthosilicate was purchased from national pharmaceutical chemicals limited, analytically pure, oxide content 28.6 wt.%. The calcination referred to in the examples below was carried out under an air atmosphere unless otherwise specified.
Inventive examples
Inventive example 1
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 2g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, simultaneously dissolving 10g of silica sol (with the solid content of 40%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 6 hours, and cooling the strips to obtain the dehydrator for the lithium ion battery electrolyte solvent, which is denoted as A1.
Inventive example 2
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5 hours to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying for 12 hours at 105 ℃, and roasting for 6.5 hours at 600 ℃ to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 3g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, simultaneously dissolving 10g of silica sol (with the solid content of 40%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 620 ℃ for 5 hours, and cooling the strips to obtain the dehydrator for the lithium ion battery electrolyte solvent, which is denoted as A2.
Inventive example 3
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 2g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, dissolving 15g of silica sol (with the solid content of 45%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 7 hours, and cooling the strips to obtain the dehydrator for the lithium ion battery electrolyte solvent, which is denoted as A3.
Inventive example 4
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5 hours to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying for 12 hours at 105 ℃, and roasting for 6.5 hours at 600 ℃ to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 3g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, simultaneously dissolving 15g of silica sol (with the solid content of 35%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 580 ℃ for 8 hours, and cooling the strips to obtain the dehydrator for the lithium ion battery electrolyte solvent, which is denoted as A4.
Inventive example 5
(S1) 9.1g of tetraethyl orthosilicate was dissolved in 175g of cyclohexane and mixed uniformly, then 105g of 4A molecular sieve powder (particle diameter of 4 μm) was added and mixed, then the mixed system was vacuumized to a vacuum degree of 50Pa and shaken and oscillated for 2.5 hours to bring the molecular sieve into full contact with the cyclohexane solution of tetraethyl orthosilicate, then dried at 105℃for 12 hours, and then calcined at 600℃for 6 hours, to obtain a modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 3g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, simultaneously dissolving 10g of silica sol (with the solid content of 40%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 6 hours, and cooling the strips to obtain the dehydrator for the lithium ion battery electrolyte solvent, which is denoted as A5.
Inventive example 6
(S1) dissolving 27.3g of tetraethyl orthosilicate in 320g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, then vacuumizing the mixed system until the vacuum degree of the mixed system is 40Pa, shaking and oscillating for 2.5 hours to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying for 12 hours at 105 ℃, and roasting for 7 hours at 600 ℃ to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 3g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, dissolving 15g of silica sol (with the solid content of 40%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 620 ℃ for 6 hours, and cooling the strips to obtain the dehydrator for the lithium ion battery electrolyte solvent, which is denoted as A6.
Inventive example 7
(S1) 36.4g of tetraethyl orthosilicate is dissolved in 400g of cyclohexane and uniformly mixed, 105g of 4A molecular sieve powder (particle size of 4 μm) is added and mixed, then the mixed system is vacuumized until the vacuum degree of the mixed system is 40Pa and shaken and oscillated for 2.5 hours to make the molecular sieve fully contact with the cyclohexane solution of the tetraethyl orthosilicate, then dried for 18 hours at 110 ℃, and then baked for 6 hours at 600 ℃ to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 3g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, dissolving 15g of silica sol (with the solid content of 40%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 6 hours, and cooling the strips to obtain the dehydrator for the lithium ion battery electrolyte solvent, which is denoted as A7.
Comparative examples
Comparative example 1
50g of 4A molecular sieve powder (particle size of 4 mu m) and 3g of sesbania powder are weighed and placed in a stirrer to be stirred for uniform mixing, meanwhile, 15g of silica sol (solid content of 40%) is dissolved in 20g of water to obtain an aqueous silica sol solution, and then the mixed aqueous silica sol solution is added into the stirrer to be stirred under the stirring condition until the mixed aqueous silica sol solution is completely and uniformly mixed, so that a mixture is obtained.
Pouring the mixture into a strip extruder, kneading, extruding the mixture from a porous die into strips, then placing the strips into an oven, drying the strips at the temperature of 105 ℃ for 12 hours, placing the strips into a muffle furnace, roasting the strips at the temperature of 600 ℃ for 6 hours, and cooling the strips to obtain the water scavenger B1.
Comparative example 2
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of ZSM-5 molecular sieve powder, mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 2.5g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, simultaneously dissolving 15g of silica sol (with the solid content of 40%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir the mixture until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 6 hours, and obtaining a water removing agent after cooling, and marking the water removing agent as B2.
Comparative example 3
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
(S2) weighing 50g of the modified molecular sieve (with the particle size of 4 mu m) and 3g of graphite powder (with the particle size of 40 meshes) in the step (S1), placing the molecular sieve and the graphite powder in a stirrer to stir uniformly, dissolving 15g of silica sol (with the solid content of 30%) in 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir completely and uniformly to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 6 hours, and obtaining a water removing agent after cooling, and marking the water removing agent as B3.
Comparative example 4
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 3g of graphite powder, putting into a stirrer, stirring to uniformly mix, dissolving 15g of silica sol (with 25% of solid content) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 6 hours, and obtaining a water removing agent after cooling, and marking the water removing agent as B4.
Comparative example 5
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 3g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, simultaneously dissolving 15g of aluminum sol (with the solid content of 30%) into 20g of water to obtain an aqueous solution of silica sol, and adding the aqueous solution of the mixed silica sol into the stirrer under the stirring condition to stir the mixture until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 6 hours, and obtaining a water removing agent after cooling, and marking the water removing agent as B5.
Comparative example 6
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
(S2) weighing 50g of the molecular sieve modified in the step (S1) and 3g of sesbania powder, putting into a stirrer for stirring to be uniformly mixed, and simultaneously putting 15g of silica-alumina sol (solid content is 20 percent, weight ratio of silica-alumina SiO 2 ：Al 2 O 3 =1:3) was dissolved in 20g of water to obtain an aqueous silica alumina sol solution, followed by stirringAdding the mixed silicon-aluminum water-soluble aqueous solution into a stirrer under the stirring condition, and stirring until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 600 ℃ for 6 hours, and obtaining a water removing agent after cooling, and marking the water removing agent as B6.
Comparative example 7
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 2g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, dissolving 15g of silica sol (with the solid content of 40%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 300 ℃ for 6 hours, and obtaining a water removing agent after cooling, and marking the water removing agent as B7.
Comparative example 8
(S1) dissolving 18.2g of tetraethyl orthosilicate in 220g of cyclohexane, uniformly mixing, then adding 105g of 4A molecular sieve powder (particle size of 4 μm) and mixing, vacuumizing the mixed system until the vacuum degree of the mixed system is 50Pa, shaking and oscillating for 2.5h to enable the molecular sieve to be fully contacted with the cyclohexane solution of the tetraethyl orthosilicate, drying at 105 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the modified molecular sieve.
And (S2) weighing 50g of the modified molecular sieve in the step (S1) and 2g of sesbania powder, putting the molecular sieve and the sesbania powder into a stirrer, stirring the mixture uniformly, dissolving 15g of silica sol (with the solid content of 40%) into 20g of water to obtain an aqueous silica sol solution, and adding the mixed aqueous silica sol solution into the stirrer under the stirring condition to stir until the mixture is completely and uniformly mixed to obtain the mixture.
(S3) pouring the mixture into a strip extruder for kneading and extruding the mixture into strips from a porous die, then placing the strips into an oven and drying the strips at the temperature of 105 ℃ for 12 hours, finally placing the strips into a muffle furnace and roasting the strips at the temperature of 700 ℃ for 6 hours, and obtaining a water removing agent after cooling, and marking the water removing agent as B8.
Test examples
Test example 1 pore size test
The water scavenger A and the unmodified 4A molecular sieve prepared in inventive example 1 were subjected to the following test, the specific test procedures of which are shown in the following Table 1 and FIGS. 1 to 3.
N 2 Adsorption isothermal adsorption curve determination: n was measured using a QUADRASORBSI adsorber from Quantachrome, inc. of America Kang Da 2 Adsorption-desorption isotherms in which the micropore volume (V mic ) Total specific surface area (S) Bet ) Obtained by a t-plot method, and the selection point range is p/p 0 =0.2 to 0.4, mesoporous volume (V meso ) From the total pore volume (V tot ) Minus the micropore volume (V) mi ) Calculated to obtain V meso ＝V tot -V mic The aperture distribution adopts BJH or DFT adsorption branch model.
NH 3 Temperature programmed desorption (NH) 3 -TPD) determination: NH was measured using an Autochem pi 2920 full-automatic temperature-programmed chemisorber from Micromeritics, inc. of America 3 During measurement, firstly tabletting and granulating the sample to 20-40 meshes, then fixing 0.1g of sample particles in the middle of a quartz tube, and activating the sample for 1h by heating up to 550 ℃ at a heating rate of 10 ℃/min under the inert gas atmosphere of carrier gas (He) with the inert gas atmosphere of 30 ml/min; then the temperature was reduced to 120℃at a rate of 10℃per minute, followed by the use of a mixed gas of ammonia and helium (volume ratio V (NH) 3 ): v (He) =15: 85 At 30 ml/min)The adsorption speed is increased for 30min, then helium He is switched to purge for 30-40 min until the baseline is stable, and NH is carried out by increasing the temperature to 700 ℃ at 10 ℃/min 3 And (3) temperature programming desorption, wherein a Thermal Conductivity Detector (TCD) is used for collecting the generated signals in the desorption process.
Table 1N 2 Pore structure parameter table obtained by adsorption and desorption data
Sample of Specific surface area (m) 2 /g) Micropore volume (cm) 3 /g) Mesoporous pore volume (cm) 3 /g)
Unmodified 4A molecular sieves 412 0.150 0.041
A1 391 0.140 0.030
N of FIG. 1 2 Adsorption-desorption isotherm plot is the direct data obtained by the adsorption apparatus, according to N 2 The data of adsorption-desorption isotherms are used for obtaining pore structure parameters and pore size distribution diagrams of the water scavenger by applying a numerical model, namely table 1 and fig. 3. Specifically, as can be seen from Table 1, the total specific surface area and pore size of the water scavenger prepared in example 1 of the present invention compared with the unmodified 4A molecular sieveThe volume is reduced, which means that a certain amount of silicon oxide is deposited on the outer surface of the molecular sieve after modification, and the modified silicon oxide has a certain modification effect on the pore canal. As can be seen from fig. 3, compared with the unmodified 4A molecular sieve, the most probable pore diameter of the water scavenger prepared in example 1 of the present invention is shifted left, i.e. the pore size of the modified molecular sieve is reduced, which indicates that a certain amount of silicon oxide deposits at the pore opening of the modified molecular sieve to have a certain modification effect on the pore channel.
In addition, from the NH of FIG. 2 3 Temperature programmed desorption (NH) 3 TPD) shows that the peak heights of the strong acid peak and the weak acid peak of the modified molecular sieve are reduced, namely NH 3 The reduction of the TPD peak area indicates the reduction of the acid amount on the outer surface of the modified molecular sieve, so that the decomposition problem caused by the catalysis of the acid on the surface of the molecular sieve when the carbonate solvent for the electrolyte of the lithium ion battery is used for removing water through the molecular sieve can be reduced to a certain extent.
Test example 2 Water removal test
The water scavengers A1 to A7 prepared in invention examples 1 to 7 and the water scavengers B1 to B8 prepared in comparative examples 1 to 8 were subjected to a single water removal experiment and a plurality of water removal experiments for recycling the solvent of the lithium ion battery electrolyte, and the test results are shown in table 2 below. The solvent of the lithium ion battery electrolyte is a commercial carbonate mixed solvent, and consists of dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1, wherein the water content is 10ppm and the purity is 99.9951 percent measured before a water removal experiment.
The single water removal experiment comprises the following specific steps: in a glove box, taking 20mL of a carbonate mixed solvent for lithium ion battery electrolyte, putting 5g of a water removing agent into a sample bottle, covering a sample bottle cover, standing for 30min, taking supernatant, and measuring the water content and purity of the carbonate mixed solvent in the sample bottle.
The specific steps of the water removal experiment for recycling for multiple times are as follows: and in a glove box, pouring out the residual supernatant in the single water removal experiment sample bottle, re-adding 20mL of unused commercial carbonate mixed solvent into the sample bottle, standing for 30min, taking the supernatant, measuring the water content and purity of the carbonate mixed solvent in the sample bottle, repeating the operation for 20 times, and testing and recycling for 20 times, wherein the water content and purity of the carbonate mixed solvent are treated by the water remover.
TABLE 2 Performance test results
As can be seen from Table 1, the water scavenger of examples 1-7 of the present invention not only has higher water removal efficiency, but also can effectively inhibit solvolysis of the electrolyte while adsorbing water as compared with the unmodified molecular sieve. Compared with the comparative examples, the water scavenger obtained by modifying the molecular sieve according to the examples of the present invention has a remarkable improvement in both the water scavenging effect and the inhibition of solvolysis of the electrolyte, particularly a particularly excellent water scavenging effect, compared with the unmodified molecular sieve. The preparation method of the invention has the advantages that the use amount and the type of raw materials such as lubricant, binder and the like and the setting of various parameters in the preparation process can influence the performance of the water scavenger, and the prepared water scavenger can effectively inhibit the solvolysis in the process of removing the electrolyte solvent, and along with the prolonging of the service time, the impurities introduced and adsorbed by the carbonate solvolysis can be correspondingly reduced. Therefore, the time of the problem of the reduction of the water removal efficiency caused by the adsorption of impurities by the molecular sieve is correspondingly delayed, so that the replacement and use frequency of the water removal agent can be obviously reduced, the use and maintenance cost of the water removal agent can be saved, and the water removal agent has an excellent application prospect.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.

Claims (3)

1. The application of the water scavenger is characterized in that the water scavenger is used for removing water from carbonate solvents of electrolyte of lithium ion batteries, and the preparation method of the water scavenger sequentially comprises the following steps:
(S1) uniformly mixing a silicon source and a solvent, then adding molecular sieve powder, mixing, vacuumizing the system until the vacuum degree is lower than 80Pa, stirring for 2-18h, drying the system at 80-120 ℃ for 6-18h, and roasting at 550-700 ℃ for 4-8h to obtain a modified molecular sieve;
(S2) uniformly mixing the modified molecular sieve obtained in the step (S1) with a binder, a lubricant and water to obtain a mixture;
(S3) carrying out molding treatment, drying and roasting on the mixture obtained in the step (S2) to obtain the water scavenger,
wherein the silicon source in the step (S1) is tetraethyl orthosilicate, the molecular sieve powder is 4A molecular sieve powder, the mass ratio of the solvent to the molecular sieve powder is (1.5-4) to 1, the mass of silicon dioxide in the silicon source accounts for 1-10% of the mass of the molecular sieve powder,
the modified molecular sieve, the binder, the lubricant and the water in the step (S2) are respectively as follows in parts by weight:
45-60 parts of modified molecular sieve
10-20 parts of adhesive
Lubricant 2-4 parts
20-30 parts of water, and the water is mixed with the water,
the lubricant is sesbania powder, the binder is silica sol, the solid content in the silica sol is 35-45%,
the conditions for firing in step (S3) are: under the air atmosphere or the oxygen atmosphere, the temperature is 550-650 ℃ and the time is 4-10h.
2. The use of a water scavenger according to claim 1, wherein the solvent in step (S1) is cyclohexane.
3. Use of a water scavenger according to claim 1, characterized in that the mass of silica in the silicon source in step (S1) is 2-8% of the mass of the molecular sieve powder.
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DE19915056A1 (en) * 1999-04-01 2000-10-05 Riedel De Haen Gmbh Organic lithium salt solutions, especially battery electrolytes, are dehydrated by contact with alkali or alkaline earth metal ion exchanged zeolite granules
CN1588687A (en) * 2004-06-30 2005-03-02 北京格林动力电源技术有限公司 Method for improving spinel lithium manganate cell volume and circulation property
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