阅读说明：本技术 一种复合氮掺杂蜂窝状多孔碳FeSe2/C的制备方法及产品 (A kind of cellular porous carbon FeSe of compound N doping2The preparation method and product of/C ) 是由 舒洪波 李明华 梁倩倩 闵豪 周颖 孙婷婷 韩明雨 胡婷 张晓晴 王先友 罗梦雪 于 2019-08-25 设计创作，主要内容包括：本申请涉及一种复合氮掺杂蜂窝状多孔碳FeSe_2/C的制备方法及通过该方法制得的产品,采用固相法制备出直径为20～100nm的FeSe_2纳米粒子原位生长在蜂窝状的碳负极材料上,形貌好,结晶度好,粒径分布均匀,导电碳网络能缓解体积膨胀,提供良好的导电网络,大大提升电池的循环稳定性,而被碳包裹的FeSe_2粒子能提升电池的放电比容量,两者复合之后得到性能优异的钾离子电池负极材料。(This application involves a kind of compound cellular porous carbon FeSe of N doping 2 The preparation method of/C and the product as made from this method, the FeSe for using solid phase method to prepare diameter as 20~100nm 2 Nanoparticle growth in situ is on cellular carbon negative pole material, and pattern is good, and better crystallinity degree, particle diameter distribution is uniform, and conductive carbon network can alleviate volume expansion, provides good conductive network, greatly promotes the cyclical stability of battery, and by the FeSe of carbon package 2 Particle can promote the specific discharge capacity of battery, the kalium ion battery negative electrode material being had excellent performance after the two is compound.)

1. a kind of cellular porous carbon FeSe of compound N doping₂The preparation method of/C, which comprises the following steps:

S1: carbon source, molysite being added in solvent and are configured to solution, is stirred evenly, and wherein iron concentration is 0.1~1mol/ L；

S2: heating step S1 acquired solution at 60~90 DEG C, generates to obtain solid after taking solvent to volatilize；

S3: step S2 obtained solid is dried and is clayed into power；

S4: solid of the step S3 after dry is placed in protective atmosphere progress 1~4h of pre-burning at 300~400 DEG C, then is placed in It is sintered 3~8h at 600~750 DEG C, obtains carbon-coated Fe₃C black powder；

S5: Fe3C black powder obtained by step S4 and selenium source are ground uniformly, carried out at 300~750 DEG C under protective atmosphere Calcining, obtains the cellular porous carbon FeSe of compound N doping₂/ C-material；

The molysite is selected from one or more of ferric nitrate, iron chloride, ferric sulfate；

The carbon source is selected from one or more of polyvinylpyrrolidone, dopamine, sucrose；

The selenium source is selected from one or more of selenium powder, selenium chloride, nitric acid selenium.

2. the cellular porous carbon FeSe of compound N doping according to claim 1₂The preparation method of/C, which is characterized in that step The heating of solution is carried out by oil bath in rapid S2.

3. the cellular porous carbon FeSe of compound N doping according to claim 1 or 2₂The preparation method of/C, feature exist In, in step S3 first to step S2 obtained solid at 50~100 DEG C solvent evaporated, obtain brown color xerogel, then at 60~ Dry 6~36h under the conditions of 100 DEG C.

4. the cellular porous carbon FeSe of compound N doping according to claim 1-3₂The preparation method of/C, it is special Sign is that the solvent is water and/or ethyl alcohol.

5. the cellular porous carbon FeSe of compound N doping according to claim 1-3₂The preparation method of/C, it is special Sign is that the protective atmosphere is the mixed gas or argon gas of nitrogen, argon gas or nitrogen and hydrogen and the mixed gas of hydrogen.

6. the cellular porous carbon FeSe of compound N doping according to claim 1-3₂The preparation method of/C, it is special Sign is that the time calcined in step S5 is 3~6h.

7. the cellular porous carbon FeSe of compound N doping according to claim 1-3₂The preparation method of/C, it is special Sign is that carbon source and the molar ratio of molysite are 1.8~2: 1 in step S1.

8. the cellular porous carbon FeSe of compound N doping according to claim 1-3₂The preparation method of/C, it is special Sign is that pre-burning and sintering process carry out in tube furnace in step S4, the gas flow rate of the protective atmosphere in tube furnace For 0.1~10L/min.

9. a kind of cellular porous carbon FeSe of compound N doping₂/ C, which is characterized in that by the described in any item systems of claim 1-8 Preparation Method is prepared.

Technical field

The application belongs to kalium ion battery technical field, more particularly, to a kind of compound cellular porous carbon of N doping FeSe₂The preparation method of/C.

Background technique

The energy is the important material base that the mankind depend on for existence and development.With the development of the mankind and pushing away for process of industrialization Into energy-consuming sharp increase, fossil energy of close concern to each other is increasingly reduced with the mankind, and the following environmental pollution is increasingly tight Weight, threatens the sustainable development of the mankind.Therefore, such as novel alternative energy source of wind energy, solar energy, nuclear energy is found gradually by people It is of interest.Since these energy effects are excessively dispersed, discontinuously, so that developing the energy storage to match with these energy and turning Parallel operation part and its associated materials become the task of top priority.In order to meet need growing to energy conversion and deposit in world wide It asks, people increasingly pay attention to green secondary cell.And in numerous secondary cell systems, lithium ion battery is because of operating voltage It is high, energy density is big, have extended cycle life, self-discharge rate is low, many merits such as environmentally protective, obtained quick development.But Lithium resource is unevenly distributed, and expensive to limit its development, the price of potassium is cheap compared with lithium very much, and potassium and lithium are in same main group, Configuration of extra-nuclear electron is similar, therefore chemical and physical features are similar, and in addition to this, potassium metal reserves are more abundant, and resource is extensive, In summary factor, the research about kalium ion battery is more and more popular.However, in kalium ion battery, the radius of potassium ionIt is far longer than lithium ion radiusThus potassium ion is embedded in abjection in the material can cause biggish volume Expansion makes material structure collapsing mixedization cause battery performance poor, therefore we design the electricity of new battery material improvement battery Chemical property.

Kalium ion battery is mainly made of positive and negative pole material, electrolyte, diaphragm etc., and wherein negative electrode material is in occupation of most important Status, be core key material, directly affect the important performances such as capacity, service life, cost, the safety of battery.Therefore, it develops High-performance negative electrode material is of great significance to the fast development of kalium ion battery and relevant industries.It studies at present more main It is graphite and porous carbon materials, transition metal oxide, sulfide, phosphide and selenides etc..The stable circulation of carbon material Property is preferable, but capacity is lower, and metallic compound can improve its capacity, but pure metallic compound cyclical stability is poor. FeSe₂Has many advantages, such as high theoretical specific capacity, highly-safe, pollution-free, in terms of lithium ion battery and sodium-ion battery Through being widely used, but there is also poorly conductive, the disadvantages of ion diffusion velocity is slow, material easy dusting, hinder material Further development.

The appearance of recent conversion reaction base negative electrode material becomes because it has many advantages, such as that safety is good, circulation is more stable The research hotspot of kalium ion battery negative electrode material, wherein FeSe₂With high theoretical specific capacity, low in raw material price, raw material It is abundant, it is environmental-friendly, it is safe and reliable the advantages that.FeSe₂It is widely used in lithium ion battery and sodium ion as negative electrode material Battery, but it is still at present problem in kalium ion battery preparation.

Summary of the invention

The technical problem to be solved by the present invention is to solve deficiency in the prior art, mixed to provide a kind of composite nitrogen Miscellaneous cellular porous carbon FeSe₂The preparation method of/C.

The technical solution adopted by the present invention to solve the technical problems is:

A kind of cellular porous carbon FeSe of compound N doping₂The preparation method of/C, comprising the following steps:

S1: carbon source, molysite being added in solvent and are configured to solution, is stirred evenly, wherein iron concentration be 0.1~ 1mol/L；

S2: heating step S1 acquired solution at 60~90 DEG C, generates to obtain solid after taking solvent to volatilize；

S3: step S2 obtained solid is dried；

S4: solid of the step S3 after dry is placed in protective atmosphere progress 1~4h of pre-burning at 300~400 DEG C, then is set It is sintered 3~8h at 600~750 DEG C, obtains carbon-coated Fe3C black powder；

S5: by Fe obtained by step S4₃C black powder and selenium source grinding are uniform, under protective atmosphere at 300~750 DEG C It is calcined, obtains the cellular porous carbon FeSe2/C material of compound N doping；

The molysite is selected from one or more of ferric nitrate, iron chloride, ferric sulfate；

The carbon source is selected from one or more of polyvinylpyrrolidone, dopamine, sucrose；

The selenium source is selected from one or more of selenium powder, selenium chloride, nitric acid selenium.

Preferably, the cellular porous carbon FeSe of compound N doping of the invention₂The preparation method of/C, solution in step S2 Heating is carried out by oil bath.

Preferably, the cellular porous carbon FeSe of compound N doping of the invention₂The preparation method of/C, first to step in step S3 Rapid S2 obtained solid solvent evaporated at 50~100 DEG C, obtains brown color xerogel, dry 6 under the conditions of 60~100 DEG C~ 36h。

Preferably, the cellular porous carbon FeSe of compound N doping of the invention₂The preparation method of/C, the solvent are water And/or ethyl alcohol.

Preferably, the cellular porous carbon FeSe of compound N doping of the invention₂The preparation method of/C, the protective atmosphere are The mixed gas or argon gas of nitrogen, argon gas or nitrogen and hydrogen and the mixed gas of hydrogen.

Preferably, the cellular porous carbon FeSe of compound N doping of the invention₂The preparation method of/C is calcined in step S5 Time is 3~6h.

Preferably, the cellular porous carbon FeSe of compound N doping of the invention₂The preparation method of/C, in step S1 carbon source with The molar ratio of molysite is 1.8~2:1.

Preferably, the cellular porous carbon FeSe of compound N doping of the invention₂The preparation method of/C, in step S4 pre-burning and Sintering process carries out in tube furnace, and the gas flow rate of the protective atmosphere is 0.1~10L/min in tube furnace.

A kind of cellular porous carbon FeSe of compound N doping₂/ C is prepared by above-mentioned preparation method.

The beneficial effects of the present invention are:

(1) FeSe that the present invention uses solid phase method to prepare diameter as 20~100nm₂Nanoparticle growth in situ is in honeycomb On the carbon negative pole material of shape, pattern is good, and better crystallinity degree, particle diameter distribution is uniform, and conductive carbon network can alleviate volume expansion, provides good Good conductive network greatly promotes the cyclical stability of battery, and by the FeSe of carbon package₂Particle can promote the electric discharge ratio of battery Capacity, the kalium ion battery negative electrode material being had excellent performance after the two is compound.

(2) preparation method that the present invention uses is with raw material sources are abundant, cheap, synthesis technology is simple and easy, peace It is complete reliable, yield height, non-environmental-pollution, applicability are wide, the advantages that being easy to repeatedly.The material of preparation has higher electric discharge specific volume It measures, have extended cycle life the advantages that high with coulombic efficiency, have a good application prospect in potassium ion energy storage and power battery field.

Detailed description of the invention

The technical solution of the application is further illustrated with reference to the accompanying drawings and examples.

Fig. 1 is FeSe in embodiment 1₂The XRD diagram of/C negative electrode material.

Fig. 2 is FeSe in embodiment 1₂The SEM of/C negative electrode material schemes.

Fig. 3 is FeSe in embodiment 1₂The TEM of/C negative electrode material schemes.

Fig. 4 is FeSe in embodiment 1₂Cycle performance figure of/C the negative electrode material under the current density of 0.1A/g.

Fig. 5 is FeSe in embodiment 1₂The charging and discharging curve figure of 1st, 2,10,20 circle of/C negative electrode material.

Specific embodiment

It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase Mutually combination.

It is described in detail the technical solution of the application below with reference to the accompanying drawings and in conjunction with the embodiments.