阅读说明：本技术 一种自组装氧化锌/磷酸锌/碳复合材料、电极及其制备方法 (A kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composite, electrode and preparation method thereof ) 是由 赵灵智 郭娅芸 于 2019-08-07 设计创作，主要内容包括：本发明涉及一种自组装氧化锌/磷酸锌/碳复合材料、电极及其制备方法,该制备方法中以锌盐、沉淀剂以及可口可乐作为原料,结合水热反应以及煅烧制备出了包含有三维褶皱状磷酸锌/碳骨架,以及负载于三维褶皱状磷酸锌/碳骨架上的氧化锌纳米颗粒的复合材料。该复合材料用于电极中时,其三维褶皱状磷酸锌/碳骨架为导电缓冲体,负载的氧化锌纳米颗粒为主要活性物质,提高了整体电极的导电性和稳定性,具有良好的电化学性能。相对于其他与三维碳材料复合的电极,本发明性能优良,工艺简单,成本低廉,具有规模化应用的潜力。(The present invention relates to a kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composites, electrode and preparation method thereof, using zinc salt, precipitating reagent and Coca-Cola as raw material in the preparation method, having prepared in conjunction with hydro-thermal reaction and calcining includes three-dimensional drape shape trbasic zinc phosphate/carbon skeleton, and the composite material for the Zinc oxide nanoparticle being carried on three-dimensional drape shape trbasic zinc phosphate/carbon skeleton.When the composite material is in electrode, three-dimensional accordion trbasic zinc phosphate/carbon skeleton is conductie buffer body, and the Zinc oxide nanoparticle of load is main active substances, improves the electric conductivity and stability of overall electrode, has good chemical property.Relative to the electrode of other and three-dimensional carbon Material cladding, function admirable of the present invention, simple process and low cost, the potentiality with scale application.)

1. a kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composite preparation method, which is characterized in that it includes the following steps,

A certain amount of zinc salt and precipitating reagent are dissolved in solvent, are dispersed with stirring to form reaction solution；

Above-mentioned reaction solution is carried out hydro-thermal reaction 4-8 hours at 80-120 DEG C, obtains presoma；

Then it is small to be placed in inert atmosphere the calcining 1-3 at 500-700 DEG C by dry above-mentioned presoma for presoma after drying When, obtain self-assembly zinc oxide/trbasic zinc phosphate/carbon composite；

Wherein, the solvent includes phosphoric acid and glucide.

2. the preparation method according to claim 1, which is characterized in that the solvent is comprising phosphoric acid and glucide Coca-Cola.

3. preparation method according to claim 1 or 2, which is characterized in that the zinc salt is Zinc diacetate dihydrate, described heavy Shallow lake agent is hexa.

4. preparation method according to claim 1 or 2, which is characterized in that in the reaction solution, the zinc salt and institute The concentration for stating precipitating reagent is 0.1 mol/L.

5. the preparation method according to claim 1, which is characterized in that before the drying, respectively with deionized water and Ethyl alcohol cleans the presoma；The condition of the drying is, the presoma is 8-16 hours dry under 60-100 degrees Celsius.

6. according to claim 1 or 5 the preparation method, which is characterized in that the condition of the calcining is by the presoma It is placed in argon atmosphere, is warming up to 600 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 2 hours.

7. the preparation method according to claim 3, which is characterized in that the temperature of the hydro-thermal reaction is 100 DEG C, and the time is 6 hours.

8. a kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composite, which is characterized in that the composite material includes three-dimensional drape Shape trbasic zinc phosphate/carbon skeleton, and the Zinc oxide nanoparticle being carried on three-dimensional drape shape trbasic zinc phosphate/carbon skeleton, the three-dimensional Carbon in accordion trbasic zinc phosphate/carbon skeleton is agraphitic carbon.

9. self-assembly zinc oxide/trbasic zinc phosphate/the carbon composite according to claim 8, which is characterized in that the three-dimensional pleat Corrugation trbasic zinc phosphate/carbon skeleton is doped with nitrogen, sulphur atom.

10. a kind of electrode, which is characterized in that the self-assembly zinc oxide/trbasic zinc phosphate of the electrode comprising claim 8-9/ Carbon composite.

Technical field

The present invention relates to field of lithium ion battery, and in particular to a kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composite, Electrode and preparation method thereof.

Background technique

The commercialization carbons negative electrode material of theoretical specific capacity low (about 372mAh/g) limits the further of lithium ion battery Development, is not able to satisfy the higher and higher demand of people.Therefore, find and prepare the lithium ion of high capacity, long-life and low cost Cell negative electrode material has become at present the important forward position direction of research and development high performance lithium ion battery material in the world.

Transition metal oxide (TMOs, M=Fe, Co, Ni and Zn etc.) has become as a kind of novel negative electrode material works as The hot spot of lower international research, and wherein zinc oxide is because its theoretical specific capacity high (978mAh/g), lithium ion diffusion coefficient are big, pacify The advantages that good perfection and rich reserves is considered as one of most promising negative electrode material.But it is faced with such as electric as cathode The low invertibity for leading to electrode reaction of sub- conductivity is bad and charge-discharge magnification performance is poor, the violent volume expansion of active material with The capacity attenuation that dusting causes, solid electrolyte interface film causes initial stage irreversible capacity loss big and system in charge and discharge process The problems such as standby at high cost, the period is long.In this regard, researchers have been devoted to by various modes improve zinc oxide as electrode Chemical property, wherein preparing zinc oxide/carbon composite is current research emphasis, especially with satisfactory mechanical property Three-dimensional carbon Material cladding.

A kind of oxidation that can be used for negative electrode of lithium ion battery is disclosed such as Chinese patent application the 201711449883.4th Zinc/carbon composite preparation method.Uniformly mixed Zn (CH is obtained by electrostatic spinning technique₃COO)₂/ PVP nanofiber Zinc oxide/carbon composite the pattern obtained after its calcination is mutually staggered to form for zinc oxide nano mitron with chain carbon phase by film Three-dimensional netted stereochemical structure.Zinc oxide/carbon composite that the invention obtains is under 0.1C current density, and discharge capacity is for the first time 826mAh/g, coulombic efficiency 96%.The invention product Preparation equipment is at high cost, is not suitable for industrialized production.

A kind of three-dimensional porous carbon for lithium an- ode is disclosed such as Chinese patent application the 201811004433.9th The preparation method of coating zinc oxide collector.By spray drying obtain presoma, after using acetylene as gaseous carbon sources, calcine three Tie up porous carbon coating zinc oxide granular materials.The invention shows stable electrochemistry after enclosing as negative electrode material circulation 150 Can, but complex process, comprehensive performance are to be improved.

Although it can be seen from the above, current research has been achieved for some progress, big in these methods It is mostly expensive, complicated and time consumption is made, extensive manufacture and business application are not suitable for.We need to find it is a kind of relatively easy, Effectively prepares the zinc oxide electrode with three-dimensional carbon Material cladding with the method for economy and solve its problems faced.

Summary of the invention

For the technical problems in the prior art, the primary purpose of the present invention is that providing a kind of self assembly oxidation Zinc/trbasic zinc phosphate/carbon composite, electrode and preparation method thereof.Based on the purpose, the present invention is at least provided the following technical solutions:

A kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composite preparation method comprising following steps,

A certain amount of zinc salt and precipitating reagent are dissolved in solvent, are dispersed with stirring to form reaction solution；

Above-mentioned reaction solution is carried out hydro-thermal reaction 4-8 hours at 80-120 DEG C, obtains presoma；

Presoma after drying, is then placed in inert atmosphere and calcines 1-3 at 500-700 DEG C by dry above-mentioned presoma Hour, obtain self-assembly zinc oxide/trbasic zinc phosphate/carbon composite；

Wherein, the solvent includes phosphoric acid and glucide.

Further, the solvent is Coca-Cola comprising phosphoric acid and glucide.

Further, the zinc salt is Zinc diacetate dihydrate, and the precipitating reagent is hexa.

Further, in the reaction solution, the concentration of the zinc salt and the precipitating reagent is 0.1 mol/L.

Further, before the drying, the presoma is cleaned with deionized water and ethyl alcohol respectively；The drying Condition is, the presoma is 8-16 hours dry under 60-100 degrees Celsius.

Further, the condition of the calcining is that the presoma is placed in argon atmosphere, with the heating speed of 5 DEG C/min Rate is warming up to 600 DEG C, keeps the temperature 2 hours.

Further, the temperature of the hydro-thermal reaction is 100 DEG C, and the time is 6 hours.

A kind of self-assembly zinc oxide/trbasic zinc phosphate/carbon composite, the composite material include three-dimensional drape shape trbasic zinc phosphate/ Carbon skeleton, and the Zinc oxide nanoparticle being carried on three-dimensional drape shape trbasic zinc phosphate/carbon skeleton, the three-dimensional drape shape phosphoric acid Carbon in zinc/carbon skeleton is agraphitic carbon.

Further, the three-dimensional drape shape trbasic zinc phosphate/carbon skeleton is doped with nitrogen, sulphur atom.

A kind of electrode, the electrode include above-mentioned self-assembly zinc oxide/trbasic zinc phosphate/carbon composite.

Compared with prior art, beneficial effects of the present invention are at least as follows:

(1) the invention discloses a kind of novel self-assembly preparation method thereof, in this method, using Coca-Cola, zinc salt and For precipitating reagent as reaction raw materials, Coca-Cola provides phosphoric acid and sugar, which provides the carbon of activation for reaction, in conjunction with Hydro-thermal reaction and calcine technology successfully bear Zinc oxide nanoparticle so that reaction be made to be easier to generate trbasic zinc phosphate and carbon It has been downloaded on three-dimensional drape shape trbasic zinc phosphate/carbon skeleton and has formd special pattern, the three-dimensional drape shape trbasic zinc phosphate/carbon skeleton doping There are nitrogen, sulphur atom.

(2) when self-assembly zinc oxide/trbasic zinc phosphate/carbon composite provided by the invention is used as electrode material, due to its tool There is three-dimensional drape shape trbasic zinc phosphate/carbon skeleton of high-specific surface area as buffer body, which increases electrode and electrolysis Contact between matter provides a large amount of reaction sites.In addition, the composite material of the special appearance as electrode, can not only lead to It crosses and provides strong conductie buffer body and enough spaces to adapt to volume change and improve electric conductivity and stability, it can also be Disperse Zinc oxide nanoparticle to a certain extent, avoids a large amount of reunions and dusting during its charge/discharge cycle.

(3) method relative to other in conjunction with three-dimensional carbon material, present invention process is simple, and preparation cost is cheap, has The potentiality of scale application.

Detailed description of the invention

Fig. 1 is the preparation flow figure for the composite material that the embodiment of the present invention 1 obtains.

Fig. 2 is XRD and the Raman figure for the composite material that the embodiment of the present invention 1, comparative example 1 and comparative example 2 obtain.

Fig. 3 is the XPS figure for the composite material that the embodiment of the present invention 1 and comparative example 1 obtain.

Fig. 4 is the SEM figure for the composite material that the embodiment of the present invention 1, comparative example 1 and comparative example 2 obtain.

Fig. 5 is the TEM figure for the composite material that the embodiment of the present invention 1 obtains.

Fig. 6 is that the composite material that the embodiment of the present invention 1, comparative example 1, comparative example 2, embodiment 2 and embodiment 3 obtain is used as Cyclic curve figure of the battery of cathode assembly under the current density of 200mA/g.

Specific embodiment

It is next below that the present invention will be further described in detail.

Specific implementation example of the invention is given below, and elaborates in conjunction with Figure of description to composite material, But the example that carries out an invention does not limit in any form the present invention.