CN105609769A - Preparation method for multi-level structured molybdenum disulfide microsphere negative electrode material of lithium battery - Google Patents
Preparation method for multi-level structured molybdenum disulfide microsphere negative electrode material of lithium battery Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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 relates to a preparation method for a multi-level structured molybdenum disulfide microsphere negative electrode material of a lithium battery. The method comprises the following steps of firstly, dissolving sodium molybdate dehydrate and urea in deionized water, and stirring the mixed solution for 15-60 minutes; secondly, dropwise adding hydrochloric acid to adjust a pH value to be 0-1, transferring the mixed solution in a reaction kettle taking polytetrafluoroethene as a substrate, preserving the mixed solution at 150-250 DEG C for 1 to 40 hours, naturally cooling the mixed solution to a room temperature, taking out the mixed solution after reaction, washing sediments after centrifugal separation, placing the mixed solution in an electrothermal blowing dry box for drying, taking out the mixed solution and placing the mixed solution in a mortar to grind into fine powder; and finally preparing the multi-level structured molybdenum disulfide microsphere negative electrode material of the lithium battery. With the adoption of a simple test method and process steps, the multi-level structured molybdenum disulfide microspheres with relatively small grain sizes (200-250 nanometers) and which are uniformly distributed are prepared, and the negative electrode material has excellent electrochemical performance.
Description
Technical field
The present invention relates to lithium ion battery cathode material and its preparation method, relate more specifically to a kind of multilevel hierarchy molybdenum bisuphide micro-The preparation method of ball lithium ion battery negative material.
Background technology
Lithium ion battery is novel as one, high energy, free of contamination electrochmical power source have been widely used in portable electric appts,The energy storage such as electric automobile and hybrid-electric car field. But along with earth resource consumes excessively and the appearance of the problems such as environmental pollution,Capacity, energy density and cycle performance to lithium ion battery are all had higher requirement. The negative material of lithium ion batteryIt is one of key determining its chemical property. At present, the theoretical capacity of the commercialization carbon negative pole material of extensive use is only372mAh/g, its market that can not meet manufacture high cycle performance, high-energy-density and high power density lithium ion batteryAsk. Therefore, find high-performance storage cathode of lithium material and become the focus of Study on Li-ion batteries using in recent years.
MoS2Be a kind of typical stratiform metal sulfide of similar graphene-structured, atomic layer is stacking with S-Mo-SS-Mo-S form,Between S-Mo-S, form by stronger covalent bonds, between S-S plane, interact by relatively weak Van der Waals force. ItsThe Van der Waals room of interlayer is conducive to the embedding of lithium ion, and can be buffered in the volumetric expansion that lithium ion deintercalation process causesProblem. Meanwhile, MoS2At occurring in nature rich content, easily preparation, environmentally safe, and as lithium ion battery negativeWhen material, having relatively high theoretical capacity (～670mAh/g) and good structural stability, is the electricity most with development prospectOne of utmost point material. But MoS2Can there is acute variation in the volume in charge and discharge process, make the inside stratiform knot of electrode materialStructure collapses fast, causes the cyclical stability of battery to reduce. In addition, due to MoS2Electrode material and electrolyte are in contact with one another,Its first charge-discharge can form SEI (solid-electrolyte-interface) film, causes active material loss, battery ratioCapacity loss. These factors have all limited MoS2Development in lithium ion battery field. Therefore, seek new MoS2Electrode materialMaterial technology of preparing is to overcome the deficiencies in the prior art, to promoting the research and development of lithium ion battery and applying significant.
Along with to MoS2The further investigation of electrode material, in order to improve MoS2The cycle life of negative material and reversible capacity, mainThere are two kinds of solution routes: the one, by MoS2Nanometer, by MoS2Crystalline size is reduced to nanoscale, and nanometer can shorten significantlyThe transmission path of lithium ion, the contact area of increase electrode and electrolyte, alleviates volumetric expansion etc., but also can cause specific areaExcessive, the problem such as first charge-discharge irreversible capacity is higher; The 2nd, the structure of special construction, mainly comprises hollow and material with carbon elementCompound etc., MoS has all been alleviated in the design of this class formation to a certain extent2Volume Changes in charge and discharge process, but activeThe load factor of material and the bulk density of electrode material are all low, thereby have limited MoS2Extensive use. Hierarchy is by onceThe self assembly of nanostructured, obtains the secondary structure that size is larger. Research shows, hierarchy both possessed nano material lithium fromSon and the short advantage of electric transmission distance, ensured again higher active material load factor, alleviated MoS simultaneously2Volume Changes,Micron, nano material advantage are separately farthest brought into play. For example, CN102701281A has reported a kind of flower-shaped curingThe preparation method of molybdenum tiny balloon, by (NH4)2MoO4、CS(NH2)2、NH2OHHCl and surfactant dissolves obtain in waterTo solution, then with acid-conditioning solution pH value to 5～6.5, then stir gained solution and move into reactor, after sealed thermostat reaction,Obtain product and reactant centrifugal drying is finally obtained to molybdenum bisuphide tiny balloon; CN104681815A has reported a kind of ballShape molybdenum bisuphide composite and its preparation method and application is that sodium molybdate and Cys are added in deionized water and mix and addHeat, cooling rear water and ethanol is washing alternately, obtains spherical molybdenum disulfide nano ball, then soaks molybdenum bisuphide with oleic acid,After by heating during the molybdenum bisuphide soaking is in inert atmosphere, obtain the coated spherical molybdenum bisuphide composite of agraphitic carbon;CN104218216A has reported a kind of molybdenum disulfide nano composite negative pole material, preparation method and its usage, its adopt mill ball withMolybdenum bisuphide carries out ball milling for the first time under inert gas shielding, obtains milled sample, then by milled sample, graphite powder with grindAbrading-ball carries out ball milling for the second time under inert gas shielding, obtains molybdenum disulfide nano combination electrode material; But above-mentioned existing skillThe ubiquitous shortcoming of art is: the multistage molybdenum bisuphide size of preparing is large, skewness, its microscopic appearance of more difficult control,Make still to exist in charge and discharge process Study of Volume Expansion, thereby limit their removal lithium embedded performance, cycle performance and high rate performance,And complicated process of preparation and production cost are high, affect the extensive use of molybdenum bisuphide negative material at lithium ion battery. Therefore say,Have in the technique of molybdenum bisuphide lithium ion battery negative material of multilevel hierarchy in preparation, effectively control the microcosmic of molybdenum bisuphidePattern is the key of improving molybdenum bisuphide negative material chemical property.
Summary of the invention
Technical problem to be solved by this invention is: provide one to have multilevel hierarchy mos2 microsphere lithium ion battery negative materialThe preparation method of material is a kind of side of preparing multilevel hierarchy mos2 microsphere lithium ion battery negative material by one step hydro thermal methodMethod, has overcome that the multistage molybdenum bisuphide size that makes in prior art is large, skewness, more difficult control molybdenum bisuphide micro-See the shortcoming of pattern, and the lithium ion battery negative material removal lithium embedded performance of preparing with it, cycle performance and high rate performance are not good,Loaded down with trivial details and the high defect of production cost of preparation technology.
Technical scheme of the present invention is:
A preparation method for multilevel hierarchy mos2 microsphere lithium ion battery negative material, comprises the steps:
By two molybdic acid hydrate sodium (Na2MoO4·2H2O) with urea (H2NCSNH2) and be dissolved in deionized water, be mixed with mixing moltenLiquid, is uniformly mixed solution 15～60min, then drips hydrochloric acid (HCl), and mixed solution pH value is adjusted to 0～1, then shouldMixed solution is transferred in the reactor taking polytetrafluoroethylene (PTFE) as substrate, and reactor is placed in to baking oven, at 150～250 DEG C, protectsTemperature 1～40h, then naturally cools to room temperature by this reactor with baking oven, takes out reacted mixed solution, after centrifugation, washesWash sediment, then be placed in electric drying oven with forced convection at 40～90 DEG C dry, after taking-up, be placed in mortar, be ground into thinPowder, finally makes multilevel hierarchy mos2 microsphere lithium ion battery negative material;
Wherein, mol ratio Na2MoO4：H2NCSNH2＝1:1～20；
Described stirring is the rotating speed of magnetic stirrer with 100～300r/min;
Described centrifugation is the rotating speed of 3000～12000r/min.
The preparation method of above-mentioned multilevel hierarchy mos2 microsphere lithium ion battery negative material, wherein involved raw material are equalBy commercially available, equipment and process used is all that those skilled in the art are known.
The invention has the beneficial effects as follows: compared with prior art, it is as follows that the inventive method has outstanding substantive distinguishing features:
Creativeness of the present invention is to utilize simple test method and processing step to prepare to have particle diameter less (200-250nm)And the multilevel hierarchy mos2 microsphere being evenly distributed, and the negative material making has outstanding chemical property.
(1), in design process of the present invention, taken into full account that microstructure and distribution of sizes are to molybdenum bisuphide chemical propertyImpact, ensureing that molybdenum bisuphide is under the prerequisite of multilevel hierarchy, optimized innovatively mos2 microsphere distribution of sizes,Particle size, makes it have larger specific area and good mechanical stability and then improves molybdenum bisuphide lithium ion battery negativeThe chemical property of material, adopts one step hydro thermal method to prepare the mos2 microsphere of multilevel hierarchy. The multistage knot that the present invention makesThe MoS of structure2The average grain diameter of microballoon is only between 200-250nm, and less particle diameter and uniformly distribution of sizes both can slow downIn charge and discharge process, thereby the Volume Changes of molybdenum bisuphide negative material improves molybdenum bisuphide negative material cycle performance, shortens simultaneouslyThe transmission path of lithium ion, thus the contact area of increase electrode and electrolyte increases molybdenum bisuphide negative material lithium storage content. CauseThis, adopt the electrochemistry of the multilevel hierarchy mos2 microsphere lithium ion battery negative material that one step hydro thermal method of the present invention makesCan be excellent.
(2) principal element that affects molybdenum bisuphide lithium ion battery negative material chemical property has the electrochemistry spy of molybdenum bisuphideProperty, the particle diameter of molybdenum bisuphide and the microstructure of molybdenum bisuphide. Wherein, molybdenum bisuphide microstructure is to lithium ion battery negativeThe chemical property of material has outstanding impact. In design process of the present invention, take into full account molybdenum bisuphide microstructure pairThe impact of its negative material chemical property, ensureing that molybdenum bisuphide is under the prerequisite of multilevel hierarchy, also further to molybdenum bisuphideInterlamellar spacing is optimized, and has adopted innovatively one step hydro thermal method technique to prepare the curing of the multilevel hierarchy of interlamellar spacing expansionMolybdenum microballoon. The flower-shaped molybdenum disulfide micro-balloon of this multilevel hierarchy being assembled by a class molybdenum disulfide lamellar structure both can stopVolume Changes in molybdenum bisuphide electrochemical reaction process and particle agglomeration, have again larger specific area, and then improve two sulphurThe electrochemical stability of changing molybdenum negative material with and lithium storage content; Meanwhile, molybdenum bisuphide interlamellar spacing (for example embodiment of expansionIn one, (002) interplanar distance expands 0.694nm to by 0.615nm) not only can shorten lithium ion in charge and discharge processTransmission path also can be for lithium ion provides more diffusion admittances and electro-chemical activity site, thereby improved molybdenum bisuphide negative pole materialThe electro-chemical activity utilization rate of material. Therefore, the present invention adopts one step hydro thermal method technique to prepare the multistage curing that interlamellar spacing expandsMolybdenum microballoon, has significantly improved the chemical property of molybdenum bisuphide lithium ion battery negative material.
(3), in design process of the present invention, taken into full account preparation cost, the cycle of multilevel hierarchy mos2 microsphere and beThe key issues such as no applicable large-scale production, adopt cheaply sodium molybdate and urea as reaction raw materials prerequisite under, utilize saltAcid solution is regulated to pH value to 0～1, the employing of novelty simple one step hydro thermal method prepare particle diameter less, be evenly distributedAnd the mos2 microsphere of the multilevel hierarchy that interlamellar spacing expands, makes the multilevel hierarchy that adopts process of the present invention finally to makeMos2 microsphere lithium ion battery negative material not only has good chemical property, also have preparation technology simple and reliable,The advantage that cost is low, with short production cycle and repetitive rate is high, thereby, be more suitable for the large-scale production of lithium ion battery negative material.
Compared with prior art, the marked improvement that the inventive method has is as follows:
(1), compared with prior art CN102701281A, CN104681815A, the inventive method has overcome in above-mentioned prior artLarge (> 0.5 μ of the size of mos2 microsphere m), pattern is inhomogeneous, causes occurring in electrochemical reaction process larger volumeChange and reunion efflorescence and then affect cyclical stability and the high rate performance of molybdenum bisuphide negative material; And large-size twoMolybdenum sulfide microballoon can make its specific area reduce, and causes the avtive spot of electrochemical reaction to reduce, and finally affects molybdenum bisuphide negativeThe lithium storage content of utmost point material and cycle performance.
(2), compared with prior art CN104218216A, it is negative that the inventive method has overcome the molybdenum bisuphide that above-mentioned prior art makesSimple, the single problem of microstructure of utmost point material. The molybdenum bisuphide material of single structure has poor mechanical stability, leadsCause the Study of Volume Expansion of molybdenum bisuphide negative material in electrochemical reaction process and still exist, the storage lithium that reduces electrode material holdsThe problems such as amount and stability.
(3) compare the inventive method with prior art CN102701281A, CN104218216A with CN104681815A and overcome systemThe problem that step complexity, length consuming time, the production cost of standby molybdenum bisuphide negative material be high, be not suitable for large-scale production.
(4) the prepared multilevel hierarchy mos2 microsphere lithium ion battery negative material of the present invention, by the control of synthesis technique,Be that 100mA/g circulated after 50 weeks in current density, the specific discharge capacity of battery can reach 550～850mAhg-1, through circulating 100Zhou Hou, the specific discharge capacity of battery still can reach 500～800mAhg-1, there is high reversible capacity and excellent cycle performance.
In a word, the inventive method is prepared multistage mos2 microsphere lithium ion battery negative material by one step hydro thermal method, overcomesLarge (> 0.5 μ of the mos2 microsphere particle diameter that makes in prior art m), size is inhomogeneous, is difficult to control its microscopic appearanceAnd structure, the lithium ion battery negative material chemical property of preparing with it is not good, and what complicated process of preparation and production cost were high lacksFall into.
Brief description of the drawings
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the X-ray diffractogram of the prepared multilevel hierarchy mos2 microsphere of the embodiment of the present invention 1.
Fig. 2 is the electron scanning micrograph of the prepared multilevel hierarchy mos2 microsphere of the embodiment of the present invention 1.
Fig. 3 is the particle diameter distribution map of the prepared multilevel hierarchy mos2 microsphere of the embodiment of the present invention 1.
Fig. 4 is the high power transmission electron microscope photo of the prepared multilevel hierarchy mos2 microsphere of the embodiment of the present invention 1.
Fig. 5 be the prepared multilevel hierarchy mos2 microsphere of the embodiment of the present invention 1 during as lithium ion battery negative material at electricityCharging and discharging curve when current density is 100mA/g.
Fig. 6 be the prepared multilevel hierarchy mos2 microsphere of the embodiment of the present invention 1 during as lithium ion battery negative material at electric currentCycle performance curve when density is 100mA/g.
Detailed description of the invention
Embodiment 1
Take two molybdic acid hydrate sodium (Na of requirement2MoO4·2H2O) with urea (H2NCSNH2) and be dissolved in deionized water, joinMake the mixed solution of sodium molybdate and urea, make sodium molybdate ammonium (Na in mixed solution2MoO4) and urea (H2NCSNH2) moleThan being controlled at 1:1, use magnetic stirrer to be uniformly mixed solution 15min with the rotating speed of 150r/min, obtain the two and mixClarification mixed solution, now dropwise splashing into mass fraction and be 37% hydrochloric acid solution, to make mixed solution pH be 1, then by this mixingSolution is transferred in the reactor taking polytetrafluoroethylene (PTFE) as substrate, and reactor is placed in to baking oven, at 150 DEG C, is incubated 4h, andAfter this reactor is naturally cooled to room temperature with baking oven, take out reacted mixed solution, with centrifugal point of the rotating speed of 3000r/minFrom reactant liquor and by deionized water to the reactant washing after centrifugal, then with the reactant after the rotating speed centrifuge washing of 3000r/min,The centrifugal sediment obtaining is placed in to electric drying oven with forced convection dry at 40 DEG C, takes out dry multilevel hierarchy molybdenum bisuphideMicroballoon, is placed in mortar and is ground into fine powder, makes thus multilevel hierarchy mos2 microsphere lithium ion battery negative material.
Using the multilevel hierarchy mos2 microsphere powder that makes as active material, carbon dust is conductive agent, and Kynoar is bondingAgent, and by multilevel hierarchy mos2 microsphere powder: the weight ratio of carbon dust: Kynoar=8:1:1 is inserted in mortar and is mixed, grindsMill evenly, then splashes into nitrogen methyl pyrrolidone solvent and is ground to pulpous state, and slurry is evenly applied on aluminium foil, then puts into 60 DEG CThermostatic drying chamber in dry 12h, dry to constant weight and use tablet press machine to depress to thin slice at 5MPa pressure, make thus multistageStructure mos2 microsphere anode plate for lithium ionic cell; Taking lithium metal as to electrode and reference electrode, the multilevel hierarchy curing makingMolybdenum microballoon anode plate for lithium ionic cell is working electrode, and 1mol/L is containing lithium hexafluoro phosphate (LiPF6) ethylene carbonate, carbonic acid diformazanEster and diethyl carbonate (volume ratio 1:1:1) mixed solution is electrolyte, and porous polypropylene is barrier film, is being full of the hand of argon gasIn casing, assemble CR2025 button cell.
Fig. 1 is the X-ray diffractogram of the prepared multilevel hierarchy mos2 microsphere of the present embodiment. Through comparison, in this figure twoThe mark pdf card of the diffraction maximum of molybdenum sulfide microballoon and molybdenum bisuphide matches, but its (002) crystal face is offset to low angle,The interplanar distance that shows the mos2 microsphere of synthesized expands.
Fig. 2 is the electron scanning micrograph of the prepared multilevel hierarchy mos2 microsphere of the present embodiment. As seen from the figure,The mos2 microsphere making by hydro-thermal reaction is shaped as the multistage microballoon that nanometer sheet assembles, and uniform particle diameter is 200～250Between nm and keeping good dispersiveness.
Fig. 3 is the particle diameter distribution map of the prepared multilevel hierarchy mos2 microsphere of the present embodiment 1. As seen from the figure, this enforcementThe prepared multilevel hierarchy mos2 microsphere particle diameter of example distributes and is normal distribution, and its average grain diameter is 233nm, and this reality is describedExecute the synthetic multilevel hierarchy mos2 microsphere particle diameter of example less and be evenly distributed.
Fig. 4 is the transmission electron microscope photo of the prepared multilevel hierarchy mos2 microsphere of the present embodiment. As seen from the figure,The prepared mos2 microsphere of the present embodiment presents obvious nano-sheet structure, and wherein (002) interplanar distance is expanded as0.694nm, meets XRD test result.
Fig. 5 be the prepared multilevel hierarchy mos2 microsphere of the present embodiment during as lithium ion battery negative material in current densityCharging and discharging curve during for 100mA/g. From this figure, the obtained multilevel hierarchy mos2 microsphere of the present embodiment electrode materialInitial charge capacity, discharge capacity be respectively 866mAh/g and 1206mAh/g.
Fig. 6 be the prepared multilevel hierarchy mos2 microsphere of the present embodiment during as lithium ion battery negative material in current densityCycle performance curve during for 100mA/g. From this figure, the prepared multilevel hierarchy mos2 microsphere process of the present embodimentWithin 100 weeks, circulating and reversible capacity reaches 653mAh/g, and its coulomb of efficiency is up to 98%, and the reversible capacity of electrode material has obtained greatlyWidth improves and stable cycle performance.
Embodiment 2
Take two molybdic acid hydrate sodium (Na2MoO of requirement4·2H2O) with urea (H2NCSNH2) and be dissolved in deionized water, joinMake the mixed solution of sodium molybdate and urea, make sodium molybdate ammonium (Na in mixed solution2MoO4) and urea (H2NCSNH2) moleThan being controlled at 1:5, use magnetic stirrer to be uniformly mixed solution 20min with the rotating speed of 150r/min, obtain the two and mixClarification mixed solution, now dropwise splashing into mass fraction and be 37% hydrochloric acid solution, to make mixed solution pH be 1, then by this mixingSolution is transferred in the reactor taking polytetrafluoroethylene (PTFE) as substrate, and reactor is placed in to baking oven, at 200 DEG C, is incubated 5h, andAfter this reactor is naturally cooled to room temperature with baking oven, take out reacted mixed solution, with centrifugal point of the rotating speed of 5000r/minFrom reactant liquor and by deionized water to the reactant washing after centrifugal, then with the reactant after the rotating speed centrifuge washing of 5000r/min,The centrifugal sediment obtaining is placed in to electric drying oven with forced convection dry at 50 DEG C, takes out dry multilevel hierarchy molybdenum bisuphideMicroballoon, is placed in mortar and is ground into fine powder, makes thus multilevel hierarchy mos2 microsphere lithium ion battery negative material.
Using the multilevel hierarchy mos2 microsphere powder that makes as active material, carbon dust is conductive agent, and Kynoar is bondingAgent, and by multilevel hierarchy mos2 microsphere powder: the weight ratio of carbon dust: Kynoar=8:1:1 is inserted in mortar and is mixed, grindsMill evenly, then splashes into nitrogen methyl pyrrolidone solvent and is ground to pulpous state, and slurry is evenly applied on aluminium foil, then puts into 60 DEG CThermostatic drying chamber in dry 12h, dry to constant weight and use tablet press machine to depress to thin slice at 5MPa pressure, make thus multistageStructure mos2 microsphere anode plate for lithium ionic cell; Taking lithium metal as to electrode and reference electrode, the multilevel hierarchy curing makingMolybdenum microballoon anode plate for lithium ionic cell is working electrode, and 1mol/L is containing lithium hexafluoro phosphate (LiPF6) ethylene carbonate, carbonic acid diformazanEster and diethyl carbonate (volume ratio 1:1:1) mixed solution is electrolyte, and porous polypropylene is barrier film, is being full of the hand of argon gasIn casing, assemble CR2025 button cell.
The prepared multilevel hierarchy mos2 microsphere of the present embodiment during as lithium ion battery negative material in current density isWhen 100mA/g, initial charge capacity, discharge capacity are respectively 785mAh/g and 1112mAh/g. The present embodiment is prepared multistageStructure mos2 microsphere reaches 614mAh/g through 100 weeks circulating and reversible capacity, and its coulomb of efficiency is up to 97%.
Embodiment 3
Take two molybdic acid hydrate sodium (Na of requirement2MoO4·2H2O) with urea (H2NCSNH2) and be dissolved in deionized water, joinMake the mixed solution of sodium molybdate and urea, make sodium molybdate ammonium (Na in mixed solution2MoO4) and urea (H2NCSNH2) moleThan being controlled at 1:10, use magnetic stirrer to be uniformly mixed solution 15min with the rotating speed of 150r/min, obtain the two and mixClarification mixed solution, now dropwise splashing into mass fraction and be 37% hydrochloric acid solution, to make mixed solution pH be 0.7, then this is mixedClose solution and transfer in the reactor taking polytetrafluoroethylene (PTFE) as substrate, reactor is placed in to baking oven, at 250 DEG C, be incubated 6h,Then this reactor is naturally cooled to room temperature with baking oven, take out reacted mixed solution, centrifugal with the rotating speed of 6000r/minSeparating reaction liquid and by deionized water to the reactant washing after centrifugal, then with the reaction after the rotating speed centrifuge washing of 6000r/minThing, is placed in electric drying oven with forced convection by the centrifugal sediment obtaining dry at 60 DEG C, takes out dry multilevel hierarchy two sulphurChange molybdenum microballoon, be placed in mortar and be ground into fine powder, make thus multilevel hierarchy mos2 microsphere lithium ion battery negative material.
Using the multilevel hierarchy mos2 microsphere powder that makes as active material, carbon dust is conductive agent, and Kynoar is bondingAgent, and by multilevel hierarchy mos2 microsphere powder: the weight ratio of carbon dust: Kynoar=8:1:1 is inserted in mortar and is mixed, grindsMill evenly, then splashes into nitrogen methyl pyrrolidone solvent and is ground to pulpous state, and slurry is evenly applied on aluminium foil, then puts into 60 DEG CThermostatic drying chamber in dry 12h, dry to constant weight and use tablet press machine to depress to thin slice at 5MPa pressure, make thus multistageStructure mos2 microsphere anode plate for lithium ionic cell; Taking lithium metal as to electrode and reference electrode, the multilevel hierarchy curing makingMolybdenum microballoon anode plate for lithium ionic cell is working electrode, and 1mol/L is containing lithium hexafluoro phosphate (LiPF6) ethylene carbonate, carbonic acid diformazanEster and diethyl carbonate (volume ratio 1:1:1) mixed solution is electrolyte, and porous polypropylene is barrier film, is being full of the hand of argon gasIn casing, assemble CR2025 button cell.
The prepared multilevel hierarchy mos2 microsphere of the present embodiment during as lithium ion battery negative material in current density isWhen 100mA/g, initial charge capacity, discharge capacity are respectively 806mAh/g and 1123mAh/g. The present embodiment is prepared multistageStructure mos2 microsphere reaches 621mAh/g through 100 weeks circulating and reversible capacity, and its coulomb of efficiency is up to 98%.
Raw material related in above-described embodiment are all by commercially available, and equipment and process used is all skills of the artArt personnel are known.
Unaccomplished matter of the present invention is known technology.
Claims (3)
1. a preparation method for multilevel hierarchy mos2 microsphere lithium ion battery negative material, is characterized by and comprise the steps:
By two molybdic acid hydrate sodium (Na2MoO4·2H2O) with urea (H2NCSNH2) and be dissolved in deionized water, be mixed with mixed solution, be uniformly mixed solution 15～60min, then drip hydrochloric acid (HCl), mixed solution pH value is adjusted to 0～1, again this mixed solution is transferred in the reactor taking polytetrafluoroethylene (PTFE) as substrate, reactor is placed in to baking oven, at 150～250 DEG C, be incubated 1～40h, then this reactor is naturally cooled to room temperature with baking oven, take out reacted mixed solution, washing precipitate after centrifugation, be placed on again in electric drying oven with forced convection dry at 40～90 DEG C, after taking-up, be placed on and in mortar, be ground into fine powder, finally make multilevel hierarchy mos2 microsphere lithium ion battery negative material,
Wherein, mol ratio Na2MoO4：H2NCSNH2=1:1～20。
2. the preparation method of multilevel hierarchy mos2 microsphere lithium ion battery negative material as claimed in claim 1, it is characterized by described stirring is the rotating speed of magnetic stirrer with 100～300r/min.
3. the preparation method of multilevel hierarchy mos2 microsphere lithium ion battery negative material as claimed in claim 1, is characterized by the rotating speed that described centrifugation is 3000～12000r/min.
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| CN109037641A (en) * | 2018-08-07 | 2018-12-18 | 河源广工大协同创新研究院 | A kind of lithium ion battery MoS2The preparation method of negative electrode material |
| CN109830670A (en) * | 2019-03-04 | 2019-05-31 | 郑州大学 | A kind of hollow sandwich type SiO of lithium ion battery negative material2/C/MoS2Hybrid microspheres |
| CN112670605A (en) * | 2020-12-23 | 2021-04-16 | 北京理工大学前沿技术研究院 | Method for regenerating graphite cathode material of waste lithium ion battery |
| CN113097466A (en) * | 2021-04-02 | 2021-07-09 | 宁波润锦环保科技有限公司 | Lithium ion battery negative electrode material MoS2Preparation method of @ CFs |
| CN113140803A (en) * | 2021-04-29 | 2021-07-20 | 天能帅福得能源股份有限公司 | Based on lamella MoS2Preparation method of high-rate lithium ion battery as anode |
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| CN106145189A (en) * | 2016-06-15 | 2016-11-23 | 青岛科技大学 | A kind of preparation method of the Auricularia shape molybdenum bisuphide of edge curl fold |
| CN106145189B (en) * | 2016-06-15 | 2017-10-31 | 青岛科技大学 | A kind of preparation method of the agaric shape molybdenum disulfide of edge curl fold |
| CN106876731A (en) * | 2017-01-23 | 2017-06-20 | 吉林大学 | A kind of molybdenum disulfide nano superstructure material and its application |
| CN109037641A (en) * | 2018-08-07 | 2018-12-18 | 河源广工大协同创新研究院 | A kind of lithium ion battery MoS2The preparation method of negative electrode material |
| CN109830670A (en) * | 2019-03-04 | 2019-05-31 | 郑州大学 | A kind of hollow sandwich type SiO of lithium ion battery negative material2/C/MoS2Hybrid microspheres |
| CN112670605A (en) * | 2020-12-23 | 2021-04-16 | 北京理工大学前沿技术研究院 | Method for regenerating graphite cathode material of waste lithium ion battery |
| CN113097466A (en) * | 2021-04-02 | 2021-07-09 | 宁波润锦环保科技有限公司 | Lithium ion battery negative electrode material MoS2Preparation method of @ CFs |
| CN113097466B (en) * | 2021-04-02 | 2023-09-01 | 山西君东新材料股份有限公司 | Negative electrode material MoS of lithium ion battery 2 Preparation method of @ CFs |
| CN113140803A (en) * | 2021-04-29 | 2021-07-20 | 天能帅福得能源股份有限公司 | Based on lamella MoS2Preparation method of high-rate lithium ion battery as anode |
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