CN113054196B - Method for modifying positive active material of lithium slurry battery - Google Patents
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Abstract
The invention discloses a method for modifying a positive electrode active material of a lithium slurry battery. Belongs to the technical field of energy storage and conversion. Which comprises the following steps: (1) preparing the concentration gradient lithium nickel cobalt manganese oxide ternary material (CGNCM). (2) Performing silane coupling agent surface modification (CGNCM) on the CGNCM materialRSX) Then carrying out ionic liquid grafting (CGNCM)RSX‑IL). (3) Reacting and coating the prepared modified CGNCM with porous graphene (HGS) to obtain a coating material CGNCMRSX‑IL@ HGS-1. (4) Preparation of amino-functionalized Ionic Liquids (IL)NH2) Simultaneously, the rHGS with a small amount of carboxyl functional groups enriched on the surface is prepared. (5) Preparation of ILNH2Modified CGNCMRSX‑IL(NH2). (6) Mixing rHGS material with CGNCMRSX‑IL(NH2)Reacting to obtain a covalent bond grafted coated composite material CGNCMRSX‑ILHGS-2. The method adopts ionic liquid and the like as a connector, improves the surface-interface binding force of the material, and simultaneously improves the structural stability; the improved effect on the structural stability of the active material in a slurry liquid flow system is obvious, and the electrochemical cycle performance of the active material is improved.
Description
Technical Field
The invention relates to a method for modifying a positive electrode active material of a lithium slurry battery, in particular to a method for modifying a positive electrode active material of a lithium slurry battery by adopting high-conductivity porous graphene (HGS) as a coating material, a concentration gradient nickel cobalt lithium manganate ternary material (CGNCM) as a matrix and Ionic Liquid (IL) or silane coupling agent(s) (II)) And the two materials are used as interface connecting materials to improve the structural stability of the active material in the flowing slurry.
The invention belongs to the technical field of energy scale storage and conversion, and particularly relates to a surface modification method for a positive electrode active material in a slurry flow battery.
Background
The lithium slurry flow battery is a novel scale energy storage technology with dual advantages of a lithium ion battery and a flow battery. The positive active material occupies a high specific gravity in the slurry battery and is a very important key material. The concentration gradient lithium nickel cobalt manganese oxide ternary material (CGNCM) is based on the original ternary material substance, and the stability of the material is improved by adjusting the concentration gradient distribution of each element in the structure. The porous graphene (HGS) is a micro-nano pore structure distributed on the surface of the graphene, and is a compromise between retention of a structural ion transmission channel and high conductivity. Relevant work of the graphene-coated nickel cobalt lithium manganate ternary material in a lithium ion battery has been studied, and the coating structure improves the structural stability of the ternary material to a certain extent. However, in a lithium slurry flow battery, the clad structure still needs to be further reinforced to cope with the complex forces to which the lithium slurry flow battery is subjected in the flowing slurry, and ensure the structural integrity and high conductive property of the lithium slurry flow battery. The invention adopts ionic liquid and the like to connect the coating layer with the active particles, ensures that the excellent performance of the active material can be fully exerted, improves the structural stability and promotes the popularization and application of the active material in other series of complex environments such as a lithium slurry flow battery and the like.
Disclosure of Invention
The invention aims to provide a novel method for modifying a positive active material of a lithium slurry battery, and particularly relates to a method for modifying a positive active material of a lithium slurry battery by adopting high-conductivity HGS (high-conductivity gas-liquid) as a coating material, CGNCM (CGNCM) as a base material and IL (IL) or IL and the base materialThe composite material is used as an interface connecting material, so that the binding force of a composite material coating interface is improved, and the structural stability of the active material in the flowing slurry is further improved.
The technical scheme adopted by the invention is as follows:
a high-conductivity HGS as coating material, CGNCM as matrix material, IL or its mixtureRn-SiX(4-n)The interface connecting material is used together to improve the binding force of the composite material coating interface and prepare the coating type composite active material with high interface binding force, and the preparation method comprises the following steps:
a method for modifying a positive electrode active material of a lithium paste battery is characterized by comprising the following steps: (1) preparing a concentration gradient lithium nickel cobalt manganese oxide ternary material CGNCM by adopting a coprecipitation method; (2) adding CGNCM into toluene for ultrasonic dispersion to obtain dispersion liquid, and adding silane coupling agentn = 1-3 is added into the dispersion liquid, heated and stirred, and finally washed in toluene, centrifuged and dried to obtain the surface-modified ternary material(ii) a (3) Will be provided withDispersing in ethanol, adding ionic liquid IL into the dispersion under nitrogen protection, heating and stirring to obtain IL-graftedA material; (4) will be provided withThe material and porous graphene HGS are mixed and dispersed in ethanol for ultrasonic treatment, then the mixture is heated and stirred, and finally the product is washed and dried to obtain the graphene material(ii) a In order to improve the strong connection effect of the coating interface, an interface covalent bond reaction is adopted; (5) adding bromopropyl amino salt and IL into ethanol in proportion, heating and refluxing under the protection of nitrogen, recrystallizing and purifying, and drying to obtain amino functionalized ionic liquid;(6) Reacting HGS in nitric acid to obtain rHGS with the surface rich in carboxyl and oxygen-containing groups; (7) to be preparedDispersing in ethanol, and mixingSlowly adding the solution into the solution under the protection of nitrogen, heating and stirring for reaction to obtain the IL graftedA material; (8) reacting rHGS material withMixing with N, N' -dicyclohexylcarbodiimide DCC, adding into DMF, performing ultrasound, heating, stirring, and reacting to obtain final product(ii) a (9) ObtainingAnda clad type connecting material; in the step (2), the ultrasonic time is 5-60 min; adding intoThe molar ratio of the CGNCM to the CGNCM is 0.1-2;wherein, R is a non-hydrolytic group comprising one or a combination of a plurality of methyl, ethyl, propyl, sulfydryl, mercaptoethyl, mercaptopropyl, vinyl, propenyl, amino, aminoethyl, aminopropyl, epoxy, cyano, halogenated alkyl, acryloxy and glycidyl ether oxypropyl, and X is a hydrolytic group comprising one or a combination of a plurality of halogen, acyloxy, alkoxy, aryloxy and acyl; stirring in the step (2, 8)The temperature and the time are 30-120 ℃ and 1-24 h; in the step (3, 7), the stirring temperature and time are 30-75 ℃ and 1-24 hours; the reaction temperature and the reaction time in the step (6) are respectively 20-70 ℃ and 0.5-6 h; adding IL andthe molar ratio of (A) to (B) is 0.1 to 3; in the step (4)The addition mass ratio of the mixed material to the HGS material is 10-200, the ultrasonic time is 5-30 min, the stirring temperature and time are 30-90 ℃, and the stirring time is 0.5-12 h; the molar ratio of the bromopropyl amino salt to the IL in the step (5) is 0.5-5; the step (7) is addedAndthe molar ratio is 0.1-3; in the step (8)And the addition mass ratio of the rHGS is 10-200.
In the step (1, 2), the CGNCM material has a structural formulaWherein 0.6 is less than or equal tox≤0.9,0.05≤y≤0.4,0.05≤zLess than or equal to 0.4, andx+y+z= 1; the particle size of the synthetic material is 0.4-10 μm; wherein, the material is spherical or sphere-like, and from the core to the surface layer, the relative content of nickel element is continuously reduced, and the relative content of cobalt and manganese element is continuously increased.
In the step (3, 5), the ionic liquid is selected from one or more of the ionic liquids with the following structural general formula,: in the formula, Z is imidazole, and Z is imidazole,pyridine or pyrrolidine, X is 1-ethyl-3-methyl, 1-propyl-3-methyl, 1-butyl-3-methyl, 1-pentyl-3-methyl, 1-hexyl-3-methyl, 1-heptyl-3-methyl, 1-octyl-3-methyl, 1-allyl-3-methyl, 1-vinyl-3-ethyl, 1-benzyl-3-methyl, 1, 3-xylyl, 1-hexadecyl-3-methyl, 1-aminoethyl-2, 3-dimethyl or 1- (3-aminopropyl) -3-methyl; y is a sulfate, hydrogen sulfate, phosphate, dihydrogen phosphate, halide, tetrafluoroborate, hexafluorophosphate, or bis-trifluoromethanesulfonimide salt.
In the step (4, 6), the HGS lamella has a diameter of 0.05-10 μm, a thickness of 0.35-20 nm, a pore diameter of 1-500 nm, and an oxygen content of 0.1-10 wt%.
The application provides an interface connection type composite positive electrode active material obtained by the modification method.
The lithium slurry battery electrode is prepared by taking the interface connection type composite positive electrode active material as a positive electrode active material.
Compared with the prior art, the method of the invention has the following advantages:
(1) according to the invention, the porous graphene is used as a coating material, so that the characteristics of high conductivity and ion transmission channel of the porous graphene are considered;
(2) the invention adopts ionic liquid and the like as connectors, improves the surface interface binding force of the material and improves the structural stability.
The method has obvious effect of improving the structural stability of the active material in a slurry liquid flow system, improves the electrochemical performance and keeps the high cycle performance of the material.
Drawings
FIG. 1 is a structural characterization XRD pattern of CGNCM in the present invention
FIG. 2 is a scanning electron micrograph of CGNCM particles in the present invention
FIG. 3 is a schematic view of the interface connection structure of the clad composite material of the present invention
Detailed Description
The invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
(1) preparing the CGNCM material by a coprecipitation method: taking nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, preparing a solution A (Ni: Co: Mn =0.9:0.1: 0) and a solution B (Ni: Co: Mn =0.45:0.25: 0.3) with the total concentration of transition metal ions of 2 mol/L; preparing 8mol/L sodium hydroxide solution, 30g/L ammonia solution I and 80g/L ammonia solution II. A5L reactor was charged with 25% by volume of ammonia solution I, and solution A was fed into the reactor at a rate of 50mL/h and ammonia solution II was fed into the reactor at a rate of 25mL/h by means of a metering pump. Simultaneously, the sodium hydroxide solution and the solution B are introduced into a storage tank of the solution A at the speed of 20mL/h for mixing and stirring evenly. And introducing argon gas into the reaction kettle for protection in the whole process, controlling the temperature in the kettle to be 55 ℃, controlling the pH =12, controlling the stirring speed to be 500r/min, adjusting the rotating speed to be 200r/min after the feeding is finished, reacting for 12h at constant temperature, and finally filtering, centrifuging, washing and drying to obtain the CGNCM precursor. Mixing the precursor and lithium hydroxide according to a molar ratio of 1:1.07, grinding and calcining, wherein the calcining procedure is that the initial temperature is increased to 450 ℃ by 3 and is kept constant for 5 hours, then the temperature is increased to 800 ℃ by 2 and is kept for 18 hours, and finally the CGNCM material is obtained after natural cooling to the room temperature.
(2) Preparing an interface connection type coating composite material 1: adding 1.0g of CGNCM material into toluene, and carrying out ultrasonic treatment for 30 min; adding 4mmol of 3-chloropropyl-trimethylsiloxane into the dispersion, heating to 90 ℃, and stirring at constant temperature for 12 hours; finally, centrifugally washing and drying in toluene to obtain the surface modified ternary material CGNCM RSX (ii) a CGNCM prepared by the above method RSX Dispersing in ethanol, simultaneously dropwise adding 6mmol of 1-ethylimidazole bromine into the ethanol dispersion under the protection of nitrogen, heating to 65 ℃, stirring for 12h, centrifuging, washing and drying to obtain the IL modified CGNCM RSX-IL A material; finally, the CGNCM prepared above is used RSX-IL Ultrasonically mixing the material and the HGS material in ethanol at a mass ratio of 20:1 for 20min, heating to 65 ℃, stirring for 6h, washing and drying to obtain a coated composite material 1 (CGNCM) RSX-IL @HGS)。
(3) Preparing an interface connection type coating composite material 2: 20mmol of bromopropylamine hydrobromide and equimolar of methylimidazole are taken and added into 50mL of ethanol, and the temperature is raised to 6Stirring at 5 deg.C for 12h, recrystallizing in ethanol, and vacuum drying at 60 deg.C to obtain amino-functionalized IL NH2 A white powder; meanwhile, carrying out mild reaction on HGS in nitric acid at 60 ℃ for 6h to obtain an rHGS material with the surface rich in a small amount of carboxyl and other oxygen-containing functional groups; the CGNCM prepared in the step 2 RSX Dispersing in ethanol while adding 6mmol of IL NH2 Slowly adding into the above CGNCM under nitrogen protection RSX Heating to 65 deg.C in ethanol dispersion, stirring for 12h, centrifuging, washing, and drying to obtain IL NH2 Modified CGNCM RSX-IL(NH2) A material; finally, the material CGNCM RSX-IL(NH2) Ultrasonically mixing with rHGS in DMF solution at a mass ratio of 20:1, adding 0.8mmol of N, N' -dicyclohexylcarbodiimide into DMF, heating to 90 ℃, stirring at constant temperature for 12h, centrifuging, washing and drying to obtain a coated composite material 2 (CGNCM) RSX-IL HGS)。
(4) Lithium metal is used as a negative electrode, and the prepared modified positive active material CGNCM RSX-IL @ HGS and CGNCM RSX- IL HGS is used as a positive electrode active material, a conventional electrolyte is used as a slurry electrolyte to assemble a slurry battery, and the slurry battery is assembled at normal temperature, and the test current density is 10 mAh/g. The primary capacity of the slurry battery is 40.34 mA.h and 51.76 mA.h respectively, and the charge-discharge capacity retention rate of 30 circles is 73.24% and 87.21%.
Example 2:
example 1 was repeated, only 3-chloropropyl-trimethylsiloxane in step 2 was changed to 3-chloroethyl-trimethylsiloxane to obtain CGNCM RSX-IL HGS is a positive electrode active material, metal lithium is a negative electrode assembly slurry battery, the first discharge capacity of the battery is tested to be 58.21 mA.h, and the charge-discharge capacity retention rate of 30 circles is 88.49%.
Example 3:
example 2 was repeated, and only the amount of 3-chloroethyl-trimethylsiloxane added in step 2 was adjusted to 6mmol, to obtain CGNCM RSX-IL HGS is used as a positive active material, metal lithium is used as a negative electrode to assemble a slurry battery, the first discharge capacity is tested to be 60.21 mA.h, and the charge-discharge capacity retention rate of 30 circles is tested to be89.14%。
Example 4:
example 3 was repeated, only the ionic liquid 1-ethylimidazole bromide in step 2 was changed to 1-methylimidazole chloride to obtain CGNCM RSX-IL HGS is used as an anode active material, and metal lithium is used as a cathode to assemble a slurry battery, the first discharge capacity of the battery is tested to be 62.09 mA.h, and the charge-discharge capacity retention rate of 30 circles is tested to be 90.31%.
Example 5:
example 4 was repeated, and only the amount of the ionic liquid 1-methylimidazolium chloride added in step 2 was adjusted to 8mmol, to obtain CGNCM RSX-IL HGS is used as a positive electrode active material, metal lithium is used as a negative electrode to assemble a slurry battery, the initial discharge capacity is tested to be 64.60 mA.h, and the charge-discharge capacity retention rate of 30 circles is 91.62%.
Example 6:
example 5 was repeated except that bromopropylamine hydrobromide and methylimidazole in step 3 were added in a molar ratio of 2:1 to obtain CGNCM RSX-IL HGS is used as a positive electrode active material, metal lithium is used as a negative electrode to assemble a slurry battery, the initial discharge capacity is tested to be 66.18 mA.h, and the charge-discharge capacity retention rate of 30 circles is 92.82%.
Example 7:
example 6 was repeated with only IL in step 3 NH2 The amount added was changed to 8mmol to obtain CGNCM RSX-IL HGS is used as an anode active material, metal lithium is used as a cathode to assemble a slurry battery, the first discharge capacity of the battery is 69.18 mA.h in charge-discharge performance test, and the charge-discharge capacity retention rate of 30 circles is 94.19%.
Example 8:
example 7 was repeated, with only the CGNCM in step 3 RSX-IL(NH2) The addition of rHGS at a mass ratio of 10:1 to obtain CGNCM RSX-IL HGS is used as an anode active material, and metal lithium is used as a cathode to assemble a slurry battery, the first discharge capacity of the battery is tested to be 72.39 mA.h, and the charge-discharge capacity retention rate of 30 circles is 95.98%.
Claims (6)
1. Modification method for positive active material of lithium slurry batteryA method, characterized in that it comprises: (1) preparing a concentration gradient lithium nickel cobalt manganese oxide ternary material CGNCM by adopting a coprecipitation method; (2) adding CGNCM into toluene for ultrasonic dispersion to obtain dispersion liquid, and then adding silane coupling agentn = 1-3 is added into the dispersion liquid, heated and stirred, and finally washed in toluene, centrifuged and dried to obtain the surface-modified ternary material(ii) a (3) Will be provided withDispersing in ethanol, adding ionic liquid IL into the dispersion under nitrogen protection, heating and stirring to obtain IL-graftedA material; (4) will be provided withThe material and porous graphene HGS are mixed and dispersed in ethanol for ultrasonic treatment, then the mixture is heated and stirred, and finally the product is washed and dried to obtain the graphene material(ii) a In order to improve the strong connection effect of the coating interface, an interface covalent bond reaction is adopted; (5) adding bromopropyl amino salt and IL into ethanol in proportion, heating and refluxing under the protection of nitrogen, recrystallizing and purifying, and drying to obtain amino functionalized ionic liquid(ii) a (6) Reacting HGS in nitric acid to obtain rHGS with the surface rich in carboxyl and oxygen-containing groups; (7) to be preparedDispersing in ethanol, and mixingSlowly adding the solution into the solution under the protection of nitrogen, heating and stirring for reaction to obtain the IL graftedA material; (8) mixing rHGS material withMixing with N, N' -dicyclohexylcarbodiimide DCC, adding into DMF, performing ultrasound, heating, stirring, and reacting to obtain final product(ii) a (9) To obtainAnda clad type connecting material; the ultrasonic time in the step (2) is 5-60 min; adding intoThe molar ratio of the CGNCM to the CGNCM is 0.1-2;wherein, R is a non-hydrolytic group comprising one or a combination of a plurality of methyl, ethyl, propyl, sulfydryl, mercaptoethyl, mercaptopropyl, vinyl, propenyl, amino, aminoethyl, aminopropyl, epoxy, cyano, halogenated alkyl, acryloxy and glycidyl ether oxypropyl, and X is a hydrolytic group comprising one or a combination of a plurality of halogen, acyloxy, alkoxy, aryloxy and acyl; the stirring temperature and time in the step (2, 8) are 30-120 ℃ and 1-24 hours; the stirring temperature and time in the step (3, 7) are 30-75 ℃ and 1-24h; the reaction temperature and the reaction time in the step (6) are respectively 20-70 ℃ and 0.5-6 h; adding IL andthe molar ratio of (A) to (B) is 0.1 to 3; in the step (4)The addition mass ratio of the mixed material to the HGS material is 10-200, the ultrasonic time is 5-30 min, the stirring temperature and time are 30-90 ℃, and the stirring time is 0.5-12 h; the molar ratio of the bromopropyl amino salt to the IL in the step (5) is 0.5-5; the step (7) is addedAndthe molar ratio is 0.1-3; in the step (8)And the addition mass ratio of the rHGS is 10-200.
2. The modification method according to claim 1, wherein in the step (1, 2), the CGNCM material has a structural formulaWherein 0.6 is less than or equal tox≤0.9,0.05≤y≤0.4,0.05≤zNot more than 0.4, andx+y+z= 1; the particle size of the synthetic material is 0.4-10 μm; wherein, the material is spherical or sphere-like, and from the core to the surface layer, the relative content of nickel element is continuously reduced, and the relative content of cobalt and manganese element is continuously increased.
3. The modification method according to claim 1, wherein in the step (3, 5), the ionic liquid is selected from ionic liquids having the following structural general formulasOne or more of the bodies may be,: wherein Z is imidazole, pyridine or pyrrolidine, X is 1-ethyl-3-methyl, 1-propyl-3-methyl, 1-butyl-3-methyl, 1-pentyl-3-methyl, 1-hexyl-3-methyl, 1-heptyl-3-methyl, 1-octyl-3-methyl, 1-allyl-3-methyl, 1-vinyl-3-ethyl, 1-benzyl-3-methyl, 1, 3-xylyl, 1-hexadecyl-3-methyl, 1-aminoethyl-2, 3-dimethyl or 1- (3-aminopropyl) -3-methyl; y is a sulfate, hydrogen sulfate, phosphate, dihydrogen phosphate, halide, tetrafluoroborate, hexafluorophosphate, or bis-trifluoromethanesulfonimide salt.
4. The modification method according to claim 1, wherein the HGS in the step (4, 6) has a lamellar diameter of 0.05 to 10 μm, a thickness of 0.35 to 20nm, a pore diameter of 1 to 500nm and an oxygen content of 0.1 to 10% by weight.
5. An interface connection type composite positive electrode active material obtained by the modification method of any one of claims 1 to 4.
6. A lithium paste battery electrode, characterized in that, the electrode is prepared by using the interface connection type composite positive electrode active material of claim 5 as a positive electrode active material.
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