阅读说明：本技术 一种锌基负极材料制备方法 (A kind of zinc-base cathode material preparation method ) 是由 刘节华 王壮壮 魏香凤 孟凡成 于 2019-09-03 设计创作，主要内容包括：本发明公开了一种锌基负极材料制备方法,属于能源储存技术领域。该发明采用离子液体辅助法合成了Zn基沸石型星型材料,并通过碳化得到了无定形Zn-N-C类星结构的锌基负极材料。碳化过程中锌、氮和微孔在原位保留,增大了材料的比表面积,提高Li<Sup>+</Sup>的储存,缩短电子和Li<Sup>+</Sup>的传递路径。克服了氧化锌导电性差,体积膨胀严重的问题,提高了材料的电导率,改善了锌基材料的结构稳定性,使其作为负极材料时具有较高的比容量和循环稳定性。并且制备工艺简单,成本低廉,对环境几乎无污染,具有广泛的应用前景。(The invention discloses a kind of zinc-base cathode material preparation methods, belong to energy storage technology field.The invention has synthesized Zn base zeolite type star-shaped material using ionic liquid auxiliary law, and has obtained the zinc-base negative electrode material of amorphous Zn-N-C class star structure by carbonization.Zinc, nitrogen and micropore retain in situ in carbonisation, increase the specific surface area of material, improve Li + Storage, shorten electronics and Li + Transmission path.Zinc oxide poorly conductive is overcome, the serious problem of volume expansion improves the conductivity of material, improves the structural stability of Zr-based materials, specific capacity with higher and cyclical stability when making it as negative electrode material.And preparation process is simple, low in cost, almost pollution-free to environment, is with a wide range of applications.)

1. a kind of zinc-base cathode material preparation method, which is characterized in that specific step is as follows:

(1) zinc salt is dissolved in organic amine solvent by a certain percentage, obtains Zn (II) base ionic liquid；

(2) it by the mixing of Zn (II) base ionic liquid and a certain proportion of water, obtains Zn (OH)₂Suspension；

(3) glyoxaline ligand is added to above-mentioned Zn (OH)₂Suspension, reaction obtain zinc-imidazole radicals molecular screen material；

(4) by above-mentioned zinc-imidazole radicals molecular screen material under atmosphere of inert gases, high-temperature calcination is carried out to get the zinc-base is arrived Negative electrode material.

2. preparation method according to claim 1, which is characterized in that metal zinc salt as described in step (1) is zinc acetate, Zinc chloride, zinc nitrate, zinc sulfate it is one or more.

3. preparation method according to claim 1, which is characterized in that organic amine solvent as described in step (1) is organic Alcohol radical amine, molecular structural formula are represented by R₁N(R₂)R₃；Wherein R₁For C_nH_2nOH (1≤n≤5), R₂,R₃For C_mH_2m+1(0≤ m≤6)。

4. preparation method according to claim 1, which is characterized in that imidazoles organic ligand as described in step (1) is Imidazoles, 1- methylimidazole, 2-methylimidazole, 1,2-methylimidazole and 4-methylimidazole it is one or more.

5. preparation method according to claim 1, which is characterized in that zinc salt, organic amine and imidazoles described in step (1) Organic ligand molar ratio is 1:(1-10): (0.1-10), wherein organic solvent and deionized water volume ratio are 1:(1-50).

6. preparation method according to claim 1, which is characterized in that the inert gas in the step (4) is nitrogen, is forged Burning temperature is 400-1200 DEG C, and heating rate is 1-50 DEG C/min, calcination time 0.5-20h.

Technical field

The invention belongs to new materials and energy storage technology field, and in particular to a kind of zinc-base cathode material preparation method.

Background technique

Lithium ion battery is widely used in mobile phone because having many advantages, such as energy density height, good cycle, computer etc. In portable device and electric car and other large-scale energy storage devices.In commercialized lithium-ion battery system, make always Use graphite as negative electrode material, but its theoretical specific capacity is only 372 mAh g^-1, limit the development of high-capacity lithium ion cell. Transition metal oxide (TMOs) lithium theory of storage capacity with higher, causes extensive note as negative electrode material of new generation Meaning.Wherein ZnO theoretical capacity is 987 mAh g^-1, lithium ion diffusion coefficient is high, and ZnO is nontoxic, and reserves are high, low cost, quilt It is considered ideal lithium ion battery negative material.However, being caused since volume acutely expands ZnO crystallite in cyclic process Electrode polarization influences electrode cycle stability, leads to capacity attenuation, and electric conductivity itself is poor, influences its high rate performance, therefore It is restricted in practical applications.

Summary of the invention

1, present invention aims at the deficiencies in the prior art are made up, a kind of novel zinc-base negative electrode material method is developed, is changed It is apt to its volume expansion problem, improves the cycle performance of zinc-base negative electrode material.

2, in order to achieve the above objectives, specific technical solution provided by the invention is as follows

A kind of zinc-base cathode material preparation method, which is characterized in that specific step is as follows:

(1) zinc salt is dissolved in organic amine solvent by a certain percentage, obtains Zn (II) base ionic liquid.

(2) it by the mixing of Zn (II) base ionic liquid and a certain proportion of water, obtains Zn (OH)₂Suspension.

(3) glyoxaline ligand is added to above-mentioned Zn (OH)₂Suspension, reaction obtain zinc-imidazole radicals molecular screen material.

(4) by above-mentioned zinc-imidazole radicals molecular screen material under atmosphere of inert gases, high-temperature calcination is carried out to get described in Zinc-base negative electrode material.

2, the metal zinc salt be zinc acetate, zinc chloride, zinc nitrate, zinc sulfate it is one or more.

3, the organic amine solvent is that its molecular structural formula is represented by R₁N(R₂)R₃.Wherein R₁For C_nH_2nOH(1≤n ≤ 5), R₂, R₃For C_mH_2m+1(0≤m≤6)。

4, the imidazoles organic ligand is imidazoles, 1- methylimidazole, 2-methylimidazole, 1,2-methylimidazole and 4- first Base imidazoles it is one or more.

5, the zinc salt, organic amine and imidazoles organic ligand molar ratio are 1:(1-10): (0.1-10), wherein organic molten Agent and deionized water volume ratio are 1:(1-50).

6, the inert gas in the step (4) is nitrogen, and calcination temperature is 400-1200 DEG C, heating rate 1-50 DEG C/min, calcination time 0.5-20h.

7, particularly advantage of the invention is:

(1) simple synthetic method is easy to operate.

(2) at low cost, raw material is wide, pollution-free.

(3) chemical property and high rate performance of zinc-base negative electrode material are improved.

8, the present invention has synthesized ZIF-Zn class star hydridization product using ionic liquid auxiliary law, and has obtained nothing by carbonization Shape Zn-N-C Microstar structure.Zinc, nitrogen and micropore retain in situ in carbonisation, improve the specific surface area of material, simultaneously Improve Li⁺Storage, shorten electronics and Li⁺Transmission path, optimize structural stability, improve and its chemical property and follow Ring performance.

Detailed description of the invention

Fig. 1 is the scanning electron microscope diagram of amorphous zinc-base negative electrode material made from present example 1.

Fig. 2 is the X-ray powder diffraction figure of amorphous zinc-base negative electrode material made from present example 1.

Fig. 3 is the cycle charge-discharge and coulombic efficiency curve of amorphous zinc-base negative electrode material made from present example 1.

Specific embodiment

It is the practicability that makes substantive distinguishing features of the invention and its have it is more readily appreciated that below in conjunction with attached drawing and several tools Body embodiment is described in further detail technical solution of the present invention.But description and explanation pair below in relation to embodiment The scope of the present invention is not limited in any way, those of ordinary skill in the art according to these embodiments made by function, side Equivalent transformation or substitution in method or structure, all belong to the scope of protection of the present invention within:

Embodiment 1

By 0.1mol zinc acetate (Zn (OAc)₂) it is added to 17.7g N, in N- dimethyl ethanolamine, 12h is stirred at room temperature and obtains Transparent uniform solution is added 267ml deionized water, continues to stir to get white uniform solution.0.1 is added in the above solution Mol 2-methylimidazole obtains white suspension, white powder solid is obtained after centrifugal drying, and above-mentioned white powder is set In tube furnace, under nitrogen atmosphere, with the heating rate of 5 DEG C/min, rises at 700 DEG C after calcining 5h and be cooled to room temperature, i.e., Obtain the amorphous zinc-base negative electrode material (Zn-N-C).

Embodiment 2

By 0.1 mol zinc chloride (ZnCl₂) be added in 17.7g ethanol amine, be stirred at room temperature 12h obtain it is transparent uniform molten Liquid is added 267ml deionized water, continues to stir to get white uniform solution.0.1 mol imidazoles is added in the above solution, obtains To white suspension, white powder solid is obtained after centrifugal drying, above-mentioned white powder is placed in tube furnace, in nitrogen Under atmosphere, with the heating rate of 5 DEG C/min, rises at 600 DEG C after calcining 5h and be cooled to room temperature to get the amorphous Zn- is arrived N-C zinc-base negative electrode material.

Embodiment 3

By 0.1mol zinc acetate (Zn (OAc)₂) be added in 17.7g ethanol amine, be stirred at room temperature 12h obtain it is transparent uniform molten Liquid is added 267ml deionized water, continues to stir to get white uniform solution.0.1mol 1- methyl miaow is added in the above solution Azoles obtains white suspension, white powder solid is obtained after centrifugal drying, and above-mentioned white powder is placed in tube furnace, Under nitrogen atmosphere, it with the heating rate of 5 DEG C/min, rises at 800 DEG C after calcining 5h and is cooled to room temperature to get the nothing is arrived Shape Zn-N-C zinc-base negative electrode material.

Embodiment 4

By 0.1mol zinc nitrate (Zn (NO₃)₂) be added in 17.7g ethanol amine liquid, be stirred at room temperature 12h obtain it is transparent One solution is added 267ml deionized water, continues to stir to get white uniform solution.0.2mol 2- first is added in the above solution Base imidazoles obtains white suspension, white powder solid is obtained after centrifugal drying, and above-mentioned white powder is placed in tube furnace In, under nitrogen atmosphere, with the heating rate of 5 DEG C/min, rises at 700 DEG C after calcining 5h and be cooled to room temperature to get described in Amorphous Zn-N-C zinc-base negative electrode material.

Embodiment 5

By 0.1mol zinc chloride (ZnCl₂) it is added to 17.7g N, in N- dimethyl ethanolamine liquid, 12h is stirred at room temperature and obtains Transparent uniform solution is added 267ml deionized water, continues to stir to get white uniform solution.It is added in the above solution 0.4mol 2-methylimidazole obtains white suspension, white powder solid is obtained after centrifugal drying, by above-mentioned white powder End is placed in tube furnace, under nitrogen atmosphere, with the heating rate of 5 DEG C/min, is risen at 700 DEG C after calcining 5h and is cooled to room Temperature to get arrive the amorphous Zn-N-C zinc-base negative electrode material.

Embodiment 6

By 0.1mol zinc chloride (ZnCl₂) it is added to 17.7g N, in N- dimethyl ethanolamine (DMEA) liquid, it is stirred at room temperature 12h obtains transparent uniform solution, and 267ml deionized water is added, continues to stir to get white uniform solution.In the above solution plus Enter 0.8 mol 2-methylimidazole, obtain white suspension, white powder solid is obtained after centrifugal drying, by above-mentioned white Powder is placed in tube furnace, under nitrogen atmosphere, with the heating rate of 5 DEG C/min, is risen at 700 DEG C after calcining 5h and is cooled to room Temperature to get arrive the amorphous Zn-N-C zinc-base negative electrode material.