CN105655543A - Metal/oxide composite negative electrode material and preparation method thereof - Google Patents
Metal/oxide composite negative electrode material and preparation method thereof Download PDFInfo
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- CN105655543A CN105655543A CN201410641569.6A CN201410641569A CN105655543A CN 105655543 A CN105655543 A CN 105655543A CN 201410641569 A CN201410641569 A CN 201410641569A CN 105655543 A CN105655543 A CN 105655543A
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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
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- 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 present invention provides a preparation method of a metal/oxide composite negative electrode material, the composite negative electrode material has a micro-nano composite-phase structure, and the preparation method is as follows: providing metal oxide powder and metal powder; mixing the metal oxide powder and the metal powder in a molar ratio of 2: 3 to 3: 1; and ball milling a mixed product with high energy. The method has the characteristics of fewer reaction steps, lower raw material requirements, and low cost, and the like, the composite negative electrode material has the micro-nano composite-phase structure, and has high specific capacity, high first-time efficiency, and good cycle performance.
Description
Technical field
The present invention relates to electrochemical power source Material Field, particularly a kind of metal/oxide Compound NegativeThe preparation method of utmost point material.
Background technology
Lithium ion battery is the novel energy storage cell growing up 21 century. Due to spies such as its high energy low consumptionsPoint, lithium ion battery has started to be widely used in the fields such as mobile phone, electric automobile, energy storage. WithCurrent development, higher to the energy density requirement of battery, especially environmental-protecting type electric automobile and Intelligent electricThe release of net energy storage, has greatly promoted the development of large capacity and high power novel battery. High-capacity lithium-ionThe research of cell negative electrode material has become with application the key that improves battery performance. In theory, some canAll can be used as lithium ion battery negative material with metal or the metalloid of lithium component alloy system. These are negativeUtmost point material is referred to as alloy material of cathode. With graphite-phase ratio, the theory storage lithium capacity of alloy material of cathode is large,Storage lithium current potential is low, has the theoretical capacity higher than graphite. In recent years, alloy anode is as Gao Rong of new generationAmount lithium ion battery negative material is subject to everybody extensive concern.
The research of alloy material of cathode mostly concentrates on the irreversible capacity and the raising that how to reduce material and followsRing aspect of performance. Reduce material granule size, can effectively reduce its body in charge and discharge processLong-pending expansion, thus capacity attenuation alleviated, improve cycle performance. In addition adopt nonactive element and active unitThe form of element formation intermetallic compound cushions the Volume Changes of alloy material of cathode, and inactive ingredients canThe cubic deformation causing when buffering lithium embedding dealkylation reaction, also can improve alloy material of cathode to a certain extentCycle performance.
At present, the main synthetic method of alloy anode has fusion method, chemical reduction method and high-energy ball milling method.Fusion method is the conventional method of preparing alloy material, by by raw metal mixing, melting, annealing in process,Obtain alloy material. Fusion method major advantage is that equipment and process is simple. Its major defect is veryRare to Nanoalloy material, and for immiscible metal on some dystectic metals and phasor,Conventional fusion method is difficult to make its alloy material. Chemical reduction method be prepare alloy superfine powder effectively andOne of conventional method. By selecting suitable complexing agent, reducing agent, can realize reduction potential comparisonThe coreduction of approaching metallic element, thus make alloy material. The major defect of chemical reduction method isLimitation is very large, the negative and larger metal of potential difference for some reduction potentials, and general reducing agent is veryDifficult by its reduction or coreduction. High-energy ball milling method is to utilize the rotation of ball mill or vibration to make hard sphere to raw materialCarry out strong shock, grinding and stirring, metal or alloy powder is pulverized to the method for nano_scale particle.Alloy powder prepared by high-energy ball milling method, its microstructure and composition distributes more even, with other physical methodsCompare, the method is simple and practical, can under comparatively gentle condition, prepare nanocrystalline metal alloy.
The various alloy materials of bibliographical information nearly all can make with high-energy ball milling method at present, but knownHigh-energy ball milling method ubiquity is easily introduced the defect of some impurity, particularly has the existence of impurity oxygen, makesNanoalloy surface in mechanical milling process is very easily oxidized. The introducing of impurity oxygen makes alloy material at embedding lithiumIn process, there is irreversible reduction decomposition reaction, thereby bring larger irreversible capacity.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of metal/oxide composite negative pole materialThe preparation method of material, by utilizing mechanical energy that high-energy ball milling provides as free energy of reaction, passes throughThe metal providing and metal oxide spontaneous reaction generate metal, and in this reduction reaction, system certainlySend out and consume impurity oxygen, can prior art in high-energy ball milling introduce impurity oxygen and bring largerThe problem of reversible capacity.
Except as otherwise noted, term " high-energy ball milling method " refers to the rotation or the vibration that utilize ball milling,Make hard sphere carry out strong shock, grinding and stirring to raw material, raw material is pulverized as nano_scale particleMethod.
Except as otherwise noted, term " micro-nano multiphase structure " refers to and has micron mutually and nanophaseThe structure of compound phase. Particularly, to refer to that nano level metal is dispersed in micro-for this micro-nano multiphase structureOn meter level matrix.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of metal/oxide composite negative pole material, described metal/oxide composite negative pole material bagDraw together: metal oxide powder, metal dust, described metal oxide powder and described metal dustMol ratio be 2:3～3:1.
Further, described metal oxide powder and described metal dust are by surface conjunction modeForm described metal/oxide composite negative pole material.
Further, described metal oxide powder particle diameter is 0.001-0.8 μ m, metal dust particle diameterFor 1-300 μ m.
Further, described metal/oxide composite negative pole material also comprises powdered graphite, described stoneThe mol ratio of ink powder end, metal oxide powder and metal dust is 0:2:3～4:3:1.
The invention provides a kind of preparation method of metal/oxide composite negative pole material, comprise following stepRapid:
(1) provide metal oxide powder and metal dust;
(2) described metal oxide powder and metal dust are mixed taking mol ratio as 2:3～3:1Close;
(3) mixed product is carried out to high-energy ball milling.
Further, described (1) also comprises provides powdered graphite, described powdered graphite, metal oxygenThe molar ratio of compound powder and metal dust is 0:2:3～4:3:1.
Further, described metal oxide powder particle diameter is 0.001-0.8 μ m, metal dust particle diameterFor 1-300 μ m.
Further, the hybird environment of described metal oxide and metal dust is inert atmosphere.
Further, described high-energy ball milling rotating speed is 300～450rpm/min.
Further, described High Energy Ball Milling Time is 0.5～40 hour.
Further, described High Energy Ball Milling Time is 8～20 hours.
Further, described high-energy ball milling pressure is 1～5MPa, and the ratio of grinding media to material of described high-energy ball milling is 20:1。
Further, described metal oxide powder is SiO2、SnO2, SnO and Sb2O3InOne or more.
Further, described metal dust is one or more in Ti, Al and Mo.
Compared with prior art, the system of a kind of metal/oxide composite negative pole material provided by the inventionPreparation Method, by utilizing mechanical energy that high-energy ball milling provides as free energy of reaction, by what provideMetal and metal oxide spontaneous reaction generate metal, the spontaneous consumption of system in this reduction reactionImpurity oxygen, solved high-energy ball milling in prior art introduce impurity oxygen and bring larger irreversibleThe problem of capacity. The present invention compared with prior art can effectively reduce the impurity in mechanical milling processOxygen, improves the advantage of efficiency first. Meanwhile, it is simple that the present invention also has synthesis technique, easily realExisting volume production, material has good micro-nano multiphase structure, is conducive to alleviate charge discharge processVolumetric expansion, there is no other by-product production, save the energy, the advantage of environmentally safe.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, below will be to realityThe accompanying drawing of executing required use in example or description of the Prior Art is briefly described, apparently, underAccompanying drawing in face description is some embodiments of the present invention, for those of ordinary skill in the art,Do not pay under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is a kind of preparation method's flow chart of metal/oxide composite negative pole material;
Fig. 2 is pure Sb before ball milling2O3With ball-milling reaction afterproduct Sb-TiO2XRD collection of illustrative plates;
Fig. 3 is pure Sb before ball milling2O3With ball-milling reaction afterproduct Sb-TiO2The XRD collection of illustrative plates of-C;
Fig. 4 a is Sb-TiO2The STEM photo of composite;
Fig. 4 b is Sb-TiO2The SEM photo of composite;
Fig. 5 is Sb-TiO2And Sb-TiO2The first charge-discharge curve of-C;
Fig. 6 is the first charge-discharge curve of a lithium ion battery embodiment.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the present inventionAccompanying drawing in embodiment, retouches clearly and completely to the technical scheme in the embodiment of the present inventionState, obviously, described embodiment is the present invention's part embodiment, instead of whole enforcementExample. Based on the embodiment in the present invention, those of ordinary skill in the art are not making creative laborThe every other embodiment obtaining under moving prerequisite, belongs to the scope of protection of the invention.
In embodiment, unreceipted specific experiment step or condition person, retouch according to the document in this areaThe operation of the normal experiment step of stating or condition can be carried out. The unreceipted production of agents useful for same or instrumentThe person of manufacturer, being can be by conventional reagent product or the instrument of commercial acquisition.
Embodiment 1. metal/oxide composite negative pole materials 1
As shown in Figure 1, the invention provides a kind of preparation side of metal/oxide composite negative pole materialMethod, concrete steps are as follows:
(101), provide metal oxide powder and metal dust;
(102), described metal oxide powder and metal dust are entered taking mol ratio as 2:3～3:1Row mixes;
(103), mixed product is carried out to high-energy ball milling.
Concrete, the Sb that is 0.001 μ m by 2 parts of particle diameters2O3Powder and 3 parts of particle diameters are 1 μ m'sTi metal dust joins in the stainless steel jar mill that argon gas and pressure are 1MPa and mixes,Because ratio of grinding media to material is 20:1, so add again the stainless steel ball of 100 parts. Above step is all at glovesIn case, carry out. To after ball grinder sealing, from glove box, take out. By high-energy ball milling tank taking rotating speed as300rpm/min turns 8 hours, and it is multiple that the product after the high-energy ball milling of last gained is metal/oxideClose negative material 1.
Embodiment 2. metal/oxide composite negative pole materials 2
The embodiment of the present invention 2 also provides a kind of preparation method of metal/oxide composite negative pole material,Its preparation process is identical with embodiment 1, and difference is, the SiO that is 0.8 μ m by 3 parts of particle diameters2PowderThe Al powder that end and 1 part of particle diameter are 300 μ m joins argon gas and pressure, and to be 5MPa stainlessIn steel ball grinding jar, mix, because ratio of grinding media to material is 20:1, so add again the stainless steel of 80 partsBall. Above step is all carried out in glove box. To after ball grinder sealing, from glove box, take out. WillHigh-energy ball milling tank turns 20 hours taking rotating speed as 450rpm/min, after the high-energy ball milling of last gainedProduct is metal/oxide composite negative pole material 2.
Embodiment 3. metal/oxide composite negative pole materials 3
The embodiment of the present invention 3 also provides a kind of preparation method of metal/oxide composite negative pole material,Its preparation process is identical with embodiment 1, and difference is, the Sb that is 0.001 μ m by 2 parts of particle diameters2O3The Ti metal dust that powder and 3 parts of particle diameters are 1 μ m and 1 part of graphite powder joined argon gas andPressure is to mix in the stainless steel jar mill of 1MPa, so add the stainless steel of 120 parts againBall. Above step is all carried out in glove box. To after ball grinder sealing, from glove box, take out. WillHigh-energy ball milling tank turns 8 hours taking rotating speed as 300rpm/min, the product after the high-energy ball milling of last gainedThing is metal/oxide composite negative pole material 3.
Embodiment 4. metal/oxide composite negative pole materials 4
The embodiment of the present invention 4 also provides a kind of preparation method of metal/oxide composite negative pole material,Its preparation process is identical with embodiment 1, and difference is, the SiO that is 0.8 μ m by 3 parts of particle diameters2PowderThe Al powder that end and 1 part of particle diameter are 300 μ m and 1 part of graphite powder have joined argon gas and pressure isIn the stainless steel jar mill of 5MPa, mix, because ratio of grinding media to material is 20:1, so add again 100The stainless steel ball of part. Above step is all carried out in glove box. By after ball grinder sealing from glove boxMiddle taking-up. High-energy ball milling tank is turned to 20 hours taking rotating speed as 300rpm/min, the height of last gainedProduct after energy ball milling is metal/oxide composite negative pole material 4.
Inventor is surprised to find that after by a large amount of tests, the mechanical energy of utilizing high-energy ball milling to provideAs free energy of reaction, under the existence of the stronger metal of the reproducibilities such as Al, Ti, Mo, canBy low thermodynamics of reactions as SiO2、SnO2、SnO、Sb2O3Deng metal oxide powder, pass throughHigh-energy ball milling spontaneous reaction generates metal Si, Sn, Sb, and then formation has answering of micro-nano phase structureClose negative material. For example,, when metal oxide is Sb2O3, when metal is Ti, metal Ti canBy Sb from Sb2O3In restore, generate TiO2, its reaction equation is as follows:
Sb2O3+3Ti→4Sb+3TiO2
Meanwhile, the metal such as Al, Ti, Mo generates Al with impurity oxygen in ball milling2O3、TiO2、MoO3Deng indifferent oxide, the reunion of metallic particles can be effectively alleviated in the existence of indifferent oxideAnd Volume Changes, reduce the irreversible capacity loss of composite diphase material in electrochemical process.
Shown in accompanying drawing 2, be pure Sb before the embodiment of the present invention 1 ball milling2O3With ball-milling reaction afterproductSb-TiO2XRD collection of illustrative plates, scanning angle is from 20～90 °. Can be found out by accompanying drawing 2, after reactionThere is Sb and TiO in product X RD collection of illustrative plates2Diffraction maximum, illustrate metal Ti by Sb from Sb2O3In restore, generate TiO simultaneously2. In mechanical milling process, reaction is as follows:
Sb2O3+3Ti→4Sb+3TiO2
Shown in accompanying drawing 3, be pure Sb before the embodiment of the present invention 3 ball millings2O3With ball-milling reaction afterproductSb-TiO2The XRD collection of illustrative plates of-C, scanning angle is from 20～90 °. Can be found out reaction by accompanying drawing 3There is the typical diffraction maximum of Sb in afterproduct XRD collection of illustrative plates, high energy ball is described under the existence of graphiteMill also can impel metal Ti by Sb from Sb2O3In restore.
Shown in accompanying drawing 4a and Fig. 4 b, be the embodiment of the present invention 1 ball-milling reaction afterproduct Sb-TiO2The high resolution scanning electromicroscopic photograph of composite and scanning transmission electron microscope photo. By accompanying drawing 4a and Fig. 4 bCan find out that nanometer Sb is evenly embedded in micron-sized TiO2Matrix surface, forms micro-nano complex phase knotStructure.
Shown in accompanying drawing 5, respectively with the product S b-after the embodiment of the present invention 1 and embodiment 3 ball millingsTiO2And Sb-TiO2-C is that active material is prepared electrode, taking lithium metal as to electrode assembling button electricityThe first charge-discharge curve in pond, test voltage is 0～2V, measuring current density is 0.1A/g. By attachedFig. 5 can find out, the efficiency first of two kinds of composites all exists remarkable improvement.
Shown in accompanying drawing 6, respectively with the product S b-after the embodiment of the present invention 1 and embodiment 3 ball millingsTiO2And Sb-TiO2-C is that active material is prepared electrode, taking lithium metal as to electrode assembling button electricityThe cycle performance curve in pond, test voltage is 0～2V, measuring current density is 0.1A/g. By accompanying drawing6 can find out, and Sb-TiO2Compare, add the composite Sb-TiO of graphite2The cyclicity of-CCan obtain remarkable improvement.
By the product metal/oxide composite negative pole material of embodiment 4 gained 4 and acetylene black and partially poly-PVF grinds and makes slurry in 1-METHYLPYRROLIDONE (NMP) medium by the mass ratio of 7:2:1Material, coating on Copper Foil, dry, section. Taking metal lithium sheet as to electrode, polypropylene screen be everyFilm, 1MLiPF6/ (EC+DMC+EMC) is electrolyte, under the current density of 0.1A/g,In the voltage range of 0.01～2V, discharge and recharge experiment. Discharge capacity is 802mAh/g first, fillsCapacitance is 696mAh/g, and coulomb efficiency is 87%, can remain on through 50 circulation volumes410mAh/g。
Finally it should be noted that: above embodiment is only in order to technical scheme of the present invention to be described, but notTo its restriction; Although the present invention is had been described in detail with reference to previous embodiment, this areaThose of ordinary skill is to be understood that: the technical scheme that it still can be recorded aforementioned each embodimentModify, or part technical characterictic is wherein equal to replacement; And these amendments or replaceChange, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technical schemes spirit andScope.
Claims (14)
1. a metal/oxide composite negative pole material, is characterized in that, described metal/oxideComposite negative pole material comprises: metal oxide powder, metal dust, described metal oxide powderWith the mol ratio of described metal dust be 2:3～3:1.
2. metal/oxide composite negative pole material according to claim 1, is characterized in that,Described metal oxide powder and described metal dust form described metal/oxygen by surface conjunction modeCompound composite negative pole material.
3. metal/oxide composite negative pole material according to claim 1, is characterized in that,Described metal oxide powder particle diameter is 0.001-0.8 μ m, and metal dust particle diameter is 1-300 μ m.
4. metal/oxide composite negative pole material according to claim 1, is characterized in that,Described metal/oxide composite negative pole material also comprises powdered graphite, described powdered graphite, metal oxygenThe mol ratio of compound powder and metal dust is 0:2:3～4:3:1.
5. a preparation method for metal/oxide composite negative pole material, comprises the following steps:
(1) provide metal oxide powder and metal dust;
(2) described metal oxide powder and metal dust are mixed taking mol ratio as 2:3～3:1Close;
(3) mixed product is carried out to high-energy ball milling.
6. method according to claim 5, is characterized in that, described (1) also comprises and carryingFor powdered graphite, the mol ratio of described powdered graphite, metal oxide powder and metal dust is0:2:3～4:3:1。
7. method according to claim 5, is characterized in that, described metal oxide powderParticle diameter is 0.001-0.8 μ m, and metal dust particle diameter is 1-300 μ m.
8. method according to claim 5, is characterized in that, described metal oxide and goldThe hybird environment that belongs to powder is inert atmosphere.
9. method according to claim 5, is characterized in that, described high-energy ball milling rotating speed is 300～450rpm/min。
10. method according to claim 5, is characterized in that, described High Energy Ball Milling TimeIt is 0.5～40 hour.
11. methods according to claim 5, is characterized in that, described High Energy Ball Milling TimeIt is 8～20 hours.
12. methods according to claim 5, is characterized in that, described high-energy ball milling pressureBe 1～5MPa, the ratio of grinding media to material of described high-energy ball milling is 20:1.
13. methods according to claim 5, is characterized in that, described metal oxide powderEnd is SiO2、SnO2, SnO and Sb2O3In one or more.
14. methods according to claim 5, is characterized in that, described metal dust be Ti,One or more in Al and Mo.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106356508A (en) * | 2016-09-29 | 2017-01-25 | 深圳市贝特瑞新能源材料股份有限公司 | Compound and preparation method thereof as well as negative electrode prepared by adopting compound and lithium ion battery |
| CN109686959A (en) * | 2019-01-03 | 2019-04-26 | 中国科学院宁波材料技术与工程研究所 | A kind of metal-modified Si oxide negative electrode material, preparation method and lithium ion battery |
| CN110311109A (en) * | 2019-06-28 | 2019-10-08 | 徐州硕祥信息科技有限公司 | A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material |
| CN111230098A (en) * | 2020-03-18 | 2020-06-05 | 北京大学 | Metal-based nano composite powder material, preparation method and application thereof |
| CN111793808A (en) * | 2020-06-23 | 2020-10-20 | 成都新柯力化工科技有限公司 | Method for industrially producing high-efficiency catalytic electrode for hydrogen production by water electrolysis |
| CN112289997A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Silicon dioxide-based composite negative electrode material for lithium ion battery and preparation method thereof |
| CN113314702A (en) * | 2021-05-27 | 2021-08-27 | 南京林业大学 | Carbon-silicon coated tin dioxide composite, preparation method thereof and application of carbon-silicon coated tin dioxide composite as lithium ion battery cathode material |
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| CN106356508A (en) * | 2016-09-29 | 2017-01-25 | 深圳市贝特瑞新能源材料股份有限公司 | Compound and preparation method thereof as well as negative electrode prepared by adopting compound and lithium ion battery |
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| CN110311109A (en) * | 2019-06-28 | 2019-10-08 | 徐州硕祥信息科技有限公司 | A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material |
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| CN111230098A (en) * | 2020-03-18 | 2020-06-05 | 北京大学 | Metal-based nano composite powder material, preparation method and application thereof |
| CN111230098B (en) * | 2020-03-18 | 2021-07-13 | 北京大学 | Metal-based nano composite powder material, preparation method and application thereof |
| CN111793808A (en) * | 2020-06-23 | 2020-10-20 | 成都新柯力化工科技有限公司 | Method for industrially producing high-efficiency catalytic electrode for hydrogen production by water electrolysis |
| CN112289997A (en) * | 2020-10-30 | 2021-01-29 | 中国科学院长春应用化学研究所 | Silicon dioxide-based composite negative electrode material for lithium ion battery and preparation method thereof |
| CN113314702A (en) * | 2021-05-27 | 2021-08-27 | 南京林业大学 | Carbon-silicon coated tin dioxide composite, preparation method thereof and application of carbon-silicon coated tin dioxide composite as lithium ion battery cathode material |
| CN113314702B (en) * | 2021-05-27 | 2022-04-12 | 南京林业大学 | Carbon-silicon coated tin dioxide composite, preparation method thereof and application of carbon-silicon coated tin dioxide composite as lithium ion battery cathode material |
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