阅读说明：本技术 一种硒-磷-碳复合材料及其制备方法与应用 (A kind of selenium-phosphorus-carbon composite and the preparation method and application thereof ) 是由 欧阳柳章 林成 刘军 胡仁宗 杨黎春 朱敏 于 2019-07-18 设计创作，主要内容包括：本发明公开了一种硒-磷-碳复合材料及其制备方法与应用。所述方法包括以下步骤：(1)将可膨胀石墨在氮气或惰性气体氛围下,800～1000℃加热5～60min,得到膨胀石墨；(2)将硒粉、红磷和膨胀石墨混合均匀,经介质阻挡放电等离子体辅助球磨处理2～45h,其中介质阻挡放电等离子体的阻挡介质为氮气或惰性气体,得到Se-P-C复合材料。该制备方法工艺简单,样品重复性好,适用于工业化大规模生产,制得的Se-P-C复合材料具有优异的储钾性能。(The invention discloses a kind of selenium-phosphorus-carbon composites and the preparation method and application thereof.The described method comprises the following steps: (1) by expansible graphite under nitrogen or atmosphere of inert gases, 800~1000 DEG C of 5~60min of heating obtain expanded graphite；(2) selenium powder, red phosphorus and expanded graphite are uniformly mixed, assist 2~45h of ball-milling treatment through dielectric barrier discharge plasma, wherein the block media of dielectric barrier discharge plasma is nitrogen or inert gas, obtains Se-P-C composite material.The preparation method simple process, sample repeatability is good, is suitable for industrialization large-scale production, and Se-P-C composite material obtained has excellent storage potassium performance.)

1. a kind of selenium-phosphorus-carbon composite preparation method, which comprises the following steps:

(1) by expansible graphite under nitrogen or atmosphere of inert gases, 800~1000 DEG C of 5~60min of heating obtain expansion stone Ink；

(2) selenium powder, red phosphorus and expanded graphite are uniformly mixed, through dielectric barrier discharge plasma auxiliary ball-milling treatment 2~ 45h, wherein the block media of dielectric barrier discharge plasma is nitrogen or inert gas, obtains Se-P-C composite material；

The molar ratio of step (2) selenium powder and red phosphorus is 1:(0.5~8), the expanded graphite accounts for Se-P-C composite material matter The 10~70% of amount.

2. a kind of selenium-phosphorus-carbon composite preparation method according to claim 1, which is characterized in that step (2) is described The molar ratio of selenium powder and red phosphorus is 1:(1~4)；The molar ratio of the selenium powder and red phosphorus is 1:(1.5~2.5)；The expansion stone Ink accounts for the 10~40% of Se-P-C composite material quality；The expanded graphite accounts for the 20~30% of Se-P-C composite material quality.

3. a kind of selenium-phosphorus-carbon composite preparation method according to claim 1 or claim 2, which is characterized in that step (2) institute It states selenium powder, red phosphorus and expanded graphite and obtains mixture after mixing, dielectric barrier discharge plasma assists ball-milling treatment institute The mass ratio of stainless steel ball and mixture is (20~100): 1, the dielectric barrier discharge plasma assists at ball milling The mass ratio of reason stainless steel ball used and mixture is (30~80): 1.

4. a kind of selenium-phosphorus-carbon composite preparation method according to claim 3, which is characterized in that the dielectric impedance It is (40~60) that discharge plasma, which assists the mass ratio of stainless steel ball used in ball-milling treatment and mixture: 1, the medium resistance The mass ratio for keeping off stainless steel ball used in discharge plasma auxiliary ball-milling treatment and mixture is (40~50): 1.

5. a kind of selenium-phosphorus-carbon composite preparation method according to claim 3, which is characterized in that step (2) is described It is 20~35h that dielectric barrier discharge plasma, which assists the time of ball-milling treatment, the dielectric barrier discharge plasma auxiliary The time of ball-milling treatment is 20~30h.

6. a kind of selenium-phosphorus-carbon composite preparation method according to claim 3, which is characterized in that step (2) is described Dielectric barrier discharge plasma assists the ball milling parameter in ball-milling treatment are as follows: ball grinder is run with the double-amplitude of 5~8mm, electricity Machine revolving speed is 900~1500r/min；It is 15kV, electric current 1 to the external voltage that ball grinder applies during ball mill vibration ~2 A, discharge frequency 60kHz；

Step (1) and (2) described inert gas are at least one of argon gas, helium, neon, Krypton, xenon and radon gas.

7. a kind of selenium-phosphorus-carbon composite made from any one of claim 1~6 the method.

8. a kind of selenium-application of the phosphorus-carbon composite in kalium ion battery field described in claim 7, which is characterized in that institute State application are as follows: by the electrode slice of selenium-phosphorus-carbon composite production kalium ion battery, specifically by selenium-phosphorus-carbon composite with Conductive agent, binder are uniformly mixed, and coating prepares electrode slice on a current collector.

9. a kind of selenium-application of the phosphorus-carbon composite in kalium ion battery field, feature exist according to claim 8 In the selenium-phosphorus-carbon composite, conductive agent and binder mass ratio is (7~8): (1~2): 1.

10. a kind of selenium-application of the phosphorus-carbon composite in kalium ion battery field, feature exist according to claim 9 In the conductive agent is conductive black, and the binder is carboxymethyl cellulose；

Selenium-phosphorus-the carbon composite also needs that solvent is added when mixing with conductive agent, binder, stirs evenly obtained slurry, so After coat on a current collector, the dosage of the solvent accounts for the 80~86.7% of stock quality, the thickness of slurry coating on a current collector Degree is 4~7 μm.

Technical field

The invention belongs to nonmetallic materials and kalium ion battery field, and in particular to a kind of selenium-phosphorus-carbon composite and its Preparation method and application.

Background technique

In the more than ten years in past, lithium ion battery has obtained relatively broad in mobile electronic device and new-energy automobile field Ground uses.However, content of the elemental lithium in the earth's crust is less, the reserves of elemental lithium can meet growing energy demand at The problem of for people's growing interest.To solve the above-mentioned problems, people always search for a kind of new secondary cell technology and go more Mend the deficiency of lithium ion battery.Kalium ion battery, which is possible to substitution lithium ion battery, becomes the energy storage device of a new generation.This be because It is relatively cheap for the price of potassium element, and reserves are almost 1000 times of elemental lithium reserves, are adapted to energy storage device increasingly The energy requirement of growth.Secondly, the standard hydrogen electrode potential (- 2.93V vs E °) of potassium element is close to lithium (- 3.04V vs E °), make it have higher operating voltage.

Although carbon based negative electrodes material graphite has certain storage potassium capability, the lower (KC of its theoretical reversible specific capacity₈, 279mA h g^-1), and high rate performance is poor.In order to solve the problems, such as that carbon-based material storage potassium capacity is lower, need to develop price Cheaply, simple process and the kalium ion battery negative electrode material that potassium is had excellent performance is stored up.Red phosphorus is held due to cheap, theoretical storage potassium Measure higher (K₃P, 2595mA h g^-1), it is very potential as storage potassium electrode material.However, the storage potassium chemical property of red phosphorus is simultaneously It is undesirable.This is because red phosphorus electric conductivity is poor and material volume changes greatly in charge and discharge process, make its circulating battery Can be poor, capacity and high rate performance are difficult to ensure.Therefore, the electric conductivity of red phosphorus negative electrode material is promoted, K is enhanced⁺In active material Intercalation/deintercalation ability, alleviate its volume expansion in charge and discharge process, for the hair of kalium ion battery phosphorus base negative electrode material Exhibition is of great significance.

Summary of the invention

To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that provide a kind of selenium-phosphorus-carbon multiple The preparation method of condensation material.

The another object of the application is to provide a kind of selenium-phosphorus-carbon composite made from the above method.The compound material Material contains Se-P nano particle and carbon coating layer.

A further object of the application is to provide a kind of above-mentioned selenium-phosphorus-carbon composite in kalium ion battery field Using.

The object of the invention is achieved through the following technical solutions:

A kind of selenium-phosphorus-carbon composite preparation method, comprising the following steps:

(1) by expansible graphite under nitrogen or atmosphere of inert gases, 800~1000 DEG C of 5~60min of heating are obtained swollen Swollen graphite；

(2) selenium powder, red phosphorus and expanded graphite are uniformly mixed, assist ball-milling treatment 2 through dielectric barrier discharge plasma ~45h, wherein the block media of dielectric barrier discharge plasma is nitrogen or inert gas, obtains Se-P-C composite material；

The molar ratio of step (2) selenium powder and red phosphorus is 1:(0.5~8), the expanded graphite accounts for Se-P-C composite wood Expect the 10~70% of quality.

Step (1) described heating temperature is preferably 1000 DEG C, and the time is preferably 15min.

Step (1) and (2) described inert gas are both preferably in argon gas, helium, neon, Krypton, xenon and radon gas extremely Few one kind.

The molar ratio of step (2) selenium powder and red phosphorus is preferably 1:(1~4), more preferably 1:(1.5~2.5)；It is described Expanded graphite accounts for the 10~40% of Se-P-C composite material quality, and more preferably 20~30%；The molar ratio of Se and P is too small, living Property particle degree of refinement is inadequate, and Se and reacting for P are incomplete；The molar ratio of Se and P is excessive, and Se and reacting for P are incomplete.

Step (2) selenium powder, red phosphorus and expanded graphite obtain mixture, dielectric barrier discharge plasma after mixing It is (20~100): 1, preferably (30~80): 1 that body, which assists the mass ratio of stainless steel ball used in ball-milling treatment and mixture,；More Preferably (40~60): 1, most preferably (40~50): 1.Ratio of grinding media to material (mass ratio of stainless steel ball and mixture) too small, ball milling Energy is smaller so that active particle degree of refinement is inadequate；Ratio of grinding media to material is excessive, and ballmilling energy falls iron powder in ball grinder Excessively, the storage potassium capacity of material is reduced.

The time of step (2) the dielectric barrier discharge plasma auxiliary ball-milling treatment is preferably 20~35h, more preferably For 20~30h.Ball-milling Time is too short, and Se reacts not exclusively with P, and active particle degree of refinement is inadequate.Ball-milling Time is too long, ball milling The iron powder of tank and abrading-ball falls excessive and wastes electric energy.Dielectric barrier discharge plasma assists ball-milling treatment, that is, dielectric impedance Discharge plasma processing and ball-milling treatment carry out simultaneously.

Ball milling parameter in step (2) dielectric barrier discharge plasma auxiliary ball-milling treatment are as follows: ball grinder with 5~ The double-amplitude of 8mm is run, and motor speed is 900~1500r/min；During ball mill vibration, to the outside of ball grinder application Voltage is 15kV, and electric current is 1~2A, discharge frequency 60kHz.

A kind of selenium-phosphorus-carbon composite made from the above method.

A kind of above-mentioned selenium-application of the phosphorus-carbon composite in kalium ion battery field.

The application are as follows: by selenium-phosphorus-carbon composite production kalium ion battery electrode slice, specifically by selenium-phosphorus-carbon Composite material is uniformly mixed with conductive agent, binder, and coating prepares electrode slice on a current collector.

The selenium-phosphorus-carbon composite, conductive agent and binder mass ratio is preferably (7~8): (1~2): 1.It is described Conductive agent is preferably conductive agent Super P (conductive black)；The binder is preferably carboxymethyl cellulose.

Selenium-phosphorus-the carbon composite also needs that solvent is added when mixing with conductive agent, binder, stirs evenly obtained slurry Material, is then coated on a current collector, and the dosage of the solvent accounts for the 80~86.7% of stock quality, and slurry coats on a current collector With a thickness of 4~7 μm.

The solvent is preferably water.

Compared with prior art, the present invention has the following advantages and beneficial effects:

(1) present invention introduces another electric conductivity better element on the basis of red phosphorus and forms phosphide, is either filling Conversion reaction either two-step reaction occurs during electric discharge, its volume expansion problem can be made to come relative to simple phosphorus It says to obtain part alleviation.

(2) there is excellent storage potassium by the Se-P-C composite material of dielectric barrier discharge plasma auxiliary ball mill preparation The entirety of material had both can be improved this is because introducing the smaller Se of storage potassium volume change in red phosphorus forms Se-P phase in performance Electric conductivity, and the volume change of active material can be alleviated by the K-Se phase and K-P phase that are formed under different potentials, also More selenides can be generated in charge and discharge process to avoid pure Se, to improve the chemical property of phosphorus base negative electrode material.

(3) high energy dielectric barrier discharge plasma of the present invention auxiliary ball milling both can preferably refinement activity Grain shortens K⁺Ion enters the shuttle path of active material, and carbon matrix can be made preferably to be formed to Se-P nano particle and wrapped It covers, further increases material overall conductivity.

(4) herein described preparation method simple process, the Se-P-C potassium that operation is efficient, controllability is strong, applied widely The preparation of ion battery cathode material, sample repeatability is good, can industrialization large-scale production.

Detailed description of the invention

Fig. 1 is the schematic diagram that dielectric barrier discharge plasma auxiliary ball mill prepares Se-P-C composite material.

Fig. 2 is the first run charging and discharging curve figure of Se-P-30wt%[email protected] composite material prepared in embodiment 1.

Fig. 3 is the SEM image of Se-2P-20wt%[email protected] composite material prepared in embodiment 2, and amplification factor is 20000:1。

Fig. 4 is the XRD spectrum of Se-2P-20wt%[email protected] composite material prepared in embodiment 2.

Fig. 5 is P- made from Se-2P-20wt%[email protected] composite material and comparative example 1 prepared in embodiment 2 The cycle performance figure of 20wt%[email protected] composite material.

Fig. 6 is the first run charging and discharging curve figure of Se-2P-20wt%[email protected] composite material prepared in embodiment 2.

Fig. 7 is the SEM image of Se-4P-20wt%[email protected] composite material prepared in embodiment 3, and amplification factor is (20000:1)。

Fig. 8 is the cycle performance figure of Se-4P-20wt%[email protected] composite material prepared in embodiment 3.

Fig. 9 is the Raman map of composite material prepared in embodiment 1,2 and 3.

Specific embodiment

Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited In this.

The embodiment of the present application is all made of the model Plasma-BM-L's of Guangzhou Chinese workers Light Electrical Science and Technology Ltd. production Dielectric barrier discharge plasma assists ball mill.

Battery used is assembled to obtain by following methods in the embodiment of the present application: using deionized water as solvent, by what is prepared Se-P-C composite material, conductive agent Super P, binder carboxymethyl cellulose are uniformly mixed according to quality proportioning 7:2:1, stirring Uniform sticky slurry is made (it is 80% that water, which accounts for stock quality ratio).Then slurry is coated uniformly on by collection by automatic coating machine On fluid copper foil, the coating thickness of slurry is 5 μm, and is put into vacuum oven and is dried in vacuo 12 hours with 80 DEG C.Dried Pole piece to strike out area with slicer be 1.13cm²Circular electric pole piece.Half-cell is assemblied in the glove box full of argon gas Middle progress, the content of oxygen and water is controlled in 0.01ppm or less in glove box.The assembling of half-cell is with circle obtained above Electrode slice is working electrode, with circular metal potassium piece be to electrode, with glass fibre (GF/D-125R, Whatman company) be every Film is assembled into CR2025 type button cell；The electrolyte used is ethylene carbonate, diethyl carbonate and KPF₆It is mixed to get Mixed liquor, wherein the solute of the mixed liquor is KPF₆(its concentration in mixed liquor is 0.8mol/L), solvent is volume ratio 1:1 Ethylene carbonate (EC) and diethyl carbonate (DEC).

Expanded graphite described in the embodiment of the present application is made by following methods: by expansible graphite under argon atmosphere, 15min is heated at 1000 DEG C, obtains expanded graphite.