CN104555983A - Subliming precipitated carbon with metallic lustre and preparation method and application of subliming precipitated carbon - Google Patents

Abstract

The invention belongs to the field of electrochemistry, and discloses a sublimation fly carbon with metallic luster, a preparation method and application thereof. The method comprises the following steps: firstly pretreating the ion exchange resin, rinsing, and drying; adding a metal salt solution, performing exchange, rinsing, and then adding the metal salt solution under _N2 atmosphere and stirring conditions, and repeating this for many times, Dry to obtain the exchange resin; perform high-temperature pyrolysis and graphitization on the exchange resin to obtain carbon powder; finally add glycine, and raise the temperature to 900-1100°C at a rate of 2-10°C/min under _N2 atmosphere, and keep it warm for 30- 120min, and then lowered to room temperature at a cooling rate of 2-10°C/min to obtain sublimed deposited carbon with metallic luster. The method of the invention is simple and low in cost; the deposited carbon can improve the activity of fuel cell catalysts and the capacity and service life of lithium ion batteries; and has good market prospect and development potential.

Description

A kind of sublimation deposited carbon with metallic luster and its preparation method and application

technical field

The invention belongs to the field of electrochemistry and relates to a method for preparing a novel carbon material, in particular to a sublimation deposited carbon with metallic luster and its preparation method and application. The carbon material can be applied to the fields of fuel cells and lithium ion batteries.

Background technique

The 21st century is the century of energy, and energy and the environment have become the themes of world development. Chemical power and energy are closely related to people's life, survival and development. Sustainable development has become the common desire and goal of mankind. However, with the improvement of people's living standards, environmental pollution has become more serious, and oil reserves are insufficient. Energy is in short supply, so it is imperative to develop technologies that replace non-renewable resources such as petroleum with electric energy. In this context, fuel cells, as a clean and efficient power generation method, have attracted worldwide attention, and all countries have carried out in-depth research. At the same time, lithium-ion batteries have attracted widespread attention as a high-efficiency energy storage device. However, the key technologies of the two still need to be improved. From the perspective of battery materials, carbon materials have important applications in fuel cells and lithium-ion batteries.

Carbon materials have important applications in the cathode and anode of fuel cells. Carbon materials as catalyst supports can greatly reduce the amount of precious metals used, thereby reducing the cost of fuel cells. The new type of cathode oxygen reduction catalyst is based on carbon materials, and it has oxygen reduction catalytic activity after direct nitrogen doping treatment.

Graphite is already a commercial anode material for lithium-ion batteries. Its stable charge and discharge performance ensures the cycle performance of lithium-ion batteries. However, with the gradual improvement of power storage capacity requirements for electrical equipment, traditional graphite can no longer meet the high-capacity requirements. Therefore, research on new carbon materials as lithium-ion battery anode materials is also a hot spot.

Contents of the invention

In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a method for preparing sublimed deposited carbon with metallic luster. The sublimation deposited carbon prepared by the invention has high graphitization degree, extremely low density and metallic luster. The most prominent feature of the preparation method of the present invention is that the polymer ion exchange resin is used as a carbon source, which sublimates during the high-temperature pyrolysis graphitization process and deposits on the tube wall to form grass-leaf-shaped graphitized carbon with metallic luster.

Another object of the present invention is to provide sublimed deposited carbon with metallic luster prepared by the above preparation method.

Another object of the present invention is to provide the application of the above-mentioned sublimation deposited carbon with metallic luster.

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

A preparation method of sublimation deposited carbon with metallic luster, specifically comprising the following steps:

(1) select ion exchange resin, carry out pretreatment to ion exchange resin;

(2) rinsing the pretreated ion exchange resin in step (1) to neutrality and drying;

(3) Add the metal salt solution to the dried ion exchange resin in step (2), exchange for 5-15 hours under _N2 atmosphere and stirring, rinse and filter until neutral; then add the metal salt solution , exchanged for 5-15 hours, rinsed and filtered until neutral, and repeated 5-10 times; finally, the resin rinsed to neutral was dried at 60-80°C for 6-12 hours to obtain an exchange resin;

(4) Put the exchange resin in step (3) into a tube furnace, and in _N2 atmosphere, heat up to 900-1100°C at a heating rate of 2-10°C/min, keep it warm for 30-120min, and then heat it up at a rate of 2-10°C/min. The cooling rate of 10°C/min is lowered to room temperature to obtain carbon powder;

(5) Ball-mill the carbon powder in step (4), then mix the ball-milled carbon powder with glycine, put it into a tube furnace, and raise the temperature at a heating rate of 2-10°C/min under _N2 atmosphere to 900-1100°C, keep warm for 30-120 minutes, and then drop to room temperature at a cooling rate of 2-10°C/min to obtain sublimed deposited carbon with metallic luster.

The ion exchange resin described in step (1) is a cation exchange resin or an anion exchange resin.

Described cation exchange resin is strongly acidic styrenic cation exchange resin, weakly acidic styrenic cation exchange resin, macroporous strongly acidic styrenic cation exchange resin or macroporous weakly acidic styrenic (acrylic acid) cation exchange resin .

The strongly acidic styrene-based cation exchange resin is more than one of 001×7, 001×4, 001×10, 001×81R or 002×7;

The macroporous strongly acidic styrene-based cation exchange resin is more than one of D001, D002, D61 or D62;

The macroporous weakly acidic styrene (acrylic) cation exchange resin is more than one of D113 or D85.

Described anion exchange resin is strongly basic styrene-based anion-exchange resin, weakly basic styrene-based anion-exchange resin, macroporous strongly basic styrene-based anion-exchange resin or macroporous weakly basic styrene-based (acrylic acid) anion exchange resin.

The strongly basic styrene-based anion exchange resin is more than one of 201×7 or 201×4;

The macroporous strongly basic styrene-based anion exchange resin is more than one of D202 or D254;

The macroporous weakly basic styrene (acrylic) anion exchange resin is more than one of D301, D311 or D318.

Described pretreatment is divided into the pretreatment of cation exchange resin and the pretreatment of anion exchange resin;

The pretreatment method of the cation exchange resin is to pretreat 5 to 20 g of the cation exchange resin with 50 to 1000 mL of acid solution for 12 to 24 hours under stirring; the concentration of the acid solution is 0.5 to 1 M (M refers to " mol/L"); the acid solution is an HCl solution; the stirring speed is 200-1000rpm;

The pretreatment method of the anion exchange resin is: under the condition of stirring, pretreat 5-20g of anion exchange resin with 50-1000mL alkali solution for 12-24h; the concentration of the alkali solution is 0.5-1M (M refers to "mol/L"); the alkaline solution is KOH solution or NaOH solution; the stirring speed is 200-1000rpm.

The rinsing in step (2) is performed with deionized water; the drying condition is drying at 60-80° C. for 6-12 hours.

The concentration of metal salt solution described in step (3) is 0.05～0.15M (M refers to "mol/L"), and the consumption ratio of described metal salt solution and ion exchange resin is (100～500) mL: (5 ~20) g;

When the ion exchange resin described in step (3) is a cation exchange resin, the metal salt solution is FeCl ₂ solution, FeCl ₃ solution, Ni(NO ₃ ) ₂ solution, NiCl ₂ solution, CoCl ₂ solution or Co(NO ₃ ) ₂ solutions; when the ion exchange resin is an anion exchange resin, one of the metal salt solution K ₃ [Fe(CN) ₆ ] solution or K ₄ [Fe(CN) ₆ ] solution above.

The stirring speed in step (3) is 400-800 rpm; the rinsing is performed with deionized water.

The ball milling time in step (5) is 1-3 hours; the mass ratio of carbon powder to glycine is 1:(6-12).

A sublimation deposited carbon with metallic luster is prepared by the above preparation method.

The application of the sublimation deposited carbon with metallic luster in fuel cell catalyst carrier, lithium ion battery negative electrode material and supercapacitor electrode material.

The sublimation deposited carbon prepared by the present invention has a metallic luster and extremely low density, and is a carbon material with a blade-like structure; the sublimed deposited carbon can be used as a fuel cell catalyst carrier and a negative electrode material of a lithium ion battery, and can improve the activity of the catalyst, Li-ion battery capacity and service life.

The carbon powder and sublimation deposited carbon prepared by the present invention contain many defects. This defect has a great impact on the performance of fuel cell catalysts, because the active sites of the oxygen reduction catalytic activity of carbon materials come from the defects of the material itself. The more defects, the more likely to build more active sites, thereby improving the activity of the catalyst. For lithium-ion batteries, the defects of negative electrode materials also contribute to the reduction of electron transfer resistance and the reduction of volume effect in the process of lithium ion intercalation and extraction, which is beneficial to the improvement of capacity and life.

In fuel cell, carbon powder and sublimation deposited carbon of the present invention can be used as anode and cathode catalyst carrier, because carbon powder and sublimation deposited carbon have certain degree of graphitization, the catalyst with it as carrier is expected to have higher Stability in electrochemical environments. After the carbon powder is treated with glycine, oxygen reduction active sites are introduced into the defective parts of the carbon powder, and it has oxygen reduction activity without loading noble metals. In lithium-ion battery negative electrode materials, graphitized sublimated deposited carbon helps The insertion of more lithium ions improves the charge and discharge capacity of lithium batteries. In the application of supercapacitors, the energy density of supercapacitors is improved by utilizing the characteristics of low density and large surface area of sublimated deposited carbon.

Compared with ordinary carbon materials, the carbon powder and sublimation deposited carbon obtained by the present invention have a simple preparation process and a short procedure, and the degree of graphitization of the obtained carbon powder and sublimated deposited carbon is significantly increased. Further exploration of supercapacitor materials has accelerated the pace.

The material prepared by the invention is mainly used in fuel cells, lithium ion batteries, supercapacitors, etc., and thus has great market prospects.

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

1. The sublimation deposited carbon prepared by the present invention is a grass blade-like carbon material containing defects, high degree of graphitization, and metallic luster; the sublimation deposited carbon can improve the activity of the catalyst, the capacity and the use of the lithium-ion battery life;

2. The preparation method of the present invention is simple, and directly obtains carbon powder and sublimation deposited carbon enriched at the top of the preparation equipment;

3. The sublimation deposited carbon prepared by the present invention is mainly used in fuel cells, lithium ion batteries, supercapacitors, etc., and has good market prospects and development potential; meanwhile, the required equipment of the present invention is simple, the reaction conditions are easy, and the cost is low. Low, easy to realize industrial production.

Description of drawings

Fig. 1 is the TEM photo of the carbon powder prepared in Example 1 and the sublimation deposited carbon with metallic luster; where a, b are the TEM photos of different magnifications of the carbon powder, c, d are the different magnifications of the sublimated deposited carbon 1 with metallic luster Multiple TEM photos;

Fig. 2 is the Raman spectrum of the carbon powder prepared in embodiment 1 and the sublimation deposition carbon with metallic luster; Wherein 1 is the Raman spectrum of carbon powder, 2 is the Raman spectrum of the sublimation deposition carbon 2 with metallic luster, 3 is the Raman spectrum of sublimated deposited carbon 3 with metallic luster;

Fig. 3 is the polarization curve of the carbon powder prepared by embodiment 1 and the sublimation deposited carbon with metallic luster as the fuel cell cathode oxygen reduction catalyst; the carbon powder is the carbon powder in the embodiment 1 step (4), and the sublimation deposited carbon 2 is Sublimated deposited carbon 2 with metallic luster, sublimated deposited carbon 3 is sublimed deposited carbon 3 with metallic luster, Pt/C is a commercial platinum carbon catalyst;

Fig. 4 is the carbon powder prepared in embodiment 1 and the sublimation deposited carbon with metallic luster as the catalytic mechanism analysis figure of fuel cell negative oxygen reduction catalyst; Wherein a is carbon powder, b is the sublimation deposited carbon 2 with metallic luster (carbon powder : Glycine mass ratio is 1:6) catalytic mechanism analysis curve, c is the catalytic mechanism analysis curve of sublimation deposited carbon 3 (carbon powder: glycine mass ratio is 1:12) with metallic luster, d is commercial platinum carbon catalyst Catalytic mechanism analysis curve;

Fig. 5 is the carbon powder prepared by embodiment 1 and the sublimation deposited carbon with metallic luster as the charge-discharge curve and cycle curve of lithium ion battery negative electrode material; Wherein a is the sublimation deposited carbon 2 (carbon powder: glycine quality) with metallic luster ratio is 1:6), b is the charge-discharge curve of sublimated deposited carbon 2 (carbon powder: glycine mass ratio is 1:6) with metallic luster; c is the cyclic voltammetry curve of carbon powder, d It is the charging and discharging curve of carbon powder.

Detailed ways

The present invention will be described in further detail below with reference to the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto.

Example 1

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 600rpm), 10g of cation exchange resin (strongly acidic styrene-based cation exchange resin 001×7) was pretreated with 0.75M HCl (500mL) for 18h;

(2) Rinse and filter the cationic resin pretreated in step (1) with deionized water until neutral, and dry at 70° C. for 8 hours;

(3) 300mL _FeCl2 solution (concentration is 0.075M) is joined in step (2) in the cation exchange resin through drying, under _N2 atmosphere and stirring (the rotating speed of stirring is 600rpm), exchange 8h, use Rinse and filter with deionized water until neutral; then add the same amount of FeCl ₂ solution, exchange for 8 hours, rinse and filter with deionized water until neutral, repeat this 7 times; finally dry the resin rinsed to neutral at 70°C 8h, obtain exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1000° C. at a heating rate of 5° C./min, keep it warm for 80 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) Active treatment of carbon powder:

0.8g of carbon powder in step (4) was ball-milled for 2 hours, and then the ball-milled carbon powder was mixed with three different contents of glycine respectively to obtain mixture 1 (the mass ratio of carbon powder: glycine was 1:8), mixture 2 (the mass ratio of carbon powder: glycine is 1:6) and mixture 3 (the mass ratio of carbon powder: glycine is 1:12); put the three mixtures into the tube furnace respectively, under _N2 atmosphere, with The temperature was raised to 1000°C at a heating rate of 5°C/min, kept at a temperature of 80 minutes, and then lowered to room temperature at a cooling rate of 5°C/min to obtain sublimated deposited carbon 1 with metallic luster, sublimated deposited carbon 2 with metallic luster, and deposited carbon with metallic luster. Glossy Sublimation Deposited Carbon 3.

The structural characterization of the prepared carbon powder, sublimated deposited carbon 1 with metallic luster, sublimated deposited carbon 2 with metallic luster and sublimated deposited carbon 3 with metallic luster are shown in Figures 1-2. These materials are used in fuel cells and For lithium-ion batteries, the performance test results are shown in Figures 3-5.

FIG. 1 is a transmission electron microscope image of the prepared carbon powder before glycine treatment (ie, carbon powder) and the carbon material after glycine treatment (ie, sublimation deposition carbon 1). It can be seen from Figure 1 that the carbon materials before and after glycine treatment are sheet-like, with a nanoscale honeycomb structure. The lattice fringes of graphite can be clearly seen in the high-resolution transmission electron microscope image, which proves that the carbon powder and sublimation deposited carbon prepared by the present invention have a good degree of graphitization. FIG. 2 is a Raman spectrum of carbon powder and sublimated deposited carbon (sublimed deposited carbon 2 and sublimated deposited carbon 3). It can be seen from Figure 2 that the Raman spectrum of carbon powder does not change much before and after glycine treatment, and there is an obvious D peak. Moreover, D/G is greater than 1, indicating that the carbon powder and sublimation deposited carbon prepared by the present invention contain more defects.

Fig. 3 is the polarization curve of sublimation deposited carbon 2, 3 and carbon powder prepared by the present invention as fuel cell cathode oxygen reduction catalyst. It can be seen from Figure 3 that the carbon powder prepared by the present invention has a certain oxygen reduction activity; after treatment with glycine, the oxygen reduction activity of sublimated carbon 2 and 3 is greatly improved, reaching a level close to that of commercial platinum catalysts. The carbon powder and sublimation deposited carbon prepared by the invention have no metal at all, let alone precious metal, and the cost is relatively low. The catalytic activity similar to that of precious metals is achieved at such a low cost, which proves that the carbon powder and sublimation deposited carbon obtained by the present invention have strong commercialization potential.

Fig. 4 is an analysis diagram of the oxygen reduction catalytic mechanism of the carbon powder of the present invention, the sublimation deposited carbon and the commercial platinum carbon catalyst. Using the rotating electrode technique, the electron transfer numbers for oxygen reduction reactions on different materials were calculated. It is concluded that the oxygen reduction reaction catalyzed by the sublimated deposited carbon of the present invention is a 4-electron process like the commercial platinum carbon catalyst. This conclusion once again proves the commercial utilization value of the product of the present invention.

Figure 5 is the charge and discharge performance curves of the lithium battery cyclic voltammetry curves of the carbon powder and sublimation deposited carbon of the present invention. It can be seen from a and c in Figure 5 that the first charge and discharge will form an SEI film, resulting in a large loss of charge and discharge capacity, but it will tend to be stable after the second charge. From b and d in Figure 5, it can be seen that the stable charge-discharge capacity of carbon powder is about 500mAhg ^-1 ; after treating the carbon powder with glycine, the stable charge-discharge capacity of sublimated deposited carbon increases to about 1200mAhg ^-1 , which is increased by 2 times many.

Example 2

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 600rpm), 15g of cation exchange resin (strongly acidic styrene-based cation exchange resin 001×7) was pretreated with 0.75M HCl (700mL) for 20h;

(2) Rinse and filter the cationic resin pretreated in step (1) with deionized water until neutral, and dry at 70° C. for 8 hours;

(3) Add 500mL Ni(NO ₃ ) ₂ solution (concentration is 0.075M) into the dried cation exchange resin in step (2), under N ₂ atmosphere and stirring (stirring speed is 600rpm), Exchange for 8 hours, rinse and filter with deionized water until neutral; then add the same amount of Ni(NO ₃ ) ₂ solution, exchange for 8 hours, rinse and filter with deionized water until neutral, repeat this 7 times; finally rinse to The neutral resin was dried at 70°C for 8 hours to obtain the exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1000° C. at a heating rate of 5° C./min, keep it warm for 80 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under _N2 atmosphere, the temperature was raised to 1000°C at a heating rate of 5°C/min, held for 80 minutes, and then lowered to room temperature at a cooling rate of 5°C/min to obtain sublimed deposited carbon with metallic luster.

Example 3

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 600rpm), 10g of cation exchange resin (strongly acidic styrene-based cation exchange resin 001×7) was pretreated with 0.85M HCl (500mL) for 16h;

(2) Rinse and filter the cationic resin pretreated in step (1) with deionized water until neutral, and dry at 70° C. for 10 h;

(3) 400mL CoCl ₂ solution (concentration is 0.075M) is joined in step (2) in the cationic exchange resin through drying, under N ₂ Atmosphere and stirring (the rotating speed of stirring is 600rpm), exchange 8h, use Rinse and filter with deionized water until neutral; then add the same amount of CoCl ₂ solution, exchange for 8 hours, rinse and filter with deionized water until neutral, repeat this 7 times; finally dry the resin rinsed to neutral at 70°C 8h, obtain exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1000° C. at a heating rate of 5° C./min, keep it warm for 80 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under _N2 atmosphere, the temperature was raised to 1000°C at a heating rate of 5°C/min, held for 80 minutes, and then lowered to room temperature at a cooling rate of 5°C/min to obtain sublimed deposited carbon with metallic luster.

Example 4

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 600rpm), 10g of cation exchange resin (macroporous strongly acidic styrene-based cation exchange resin D001) was pretreated with 0.75M HCl (500mL) for 18h;

(2) Rinse and filter the cationic resin pretreated in step (1) with deionized water until neutral, and dry at 70° C. for 8 hours;

(3) 300mL _FeCl2 solution (concentration is 0.075M) is joined in step (2) in the cation exchange resin through drying, under _N2 atmosphere and stirring (the rotating speed of stirring is 600rpm), exchange 8h, use Rinse and filter with deionized water until neutral; then add the same amount of FeCl ₂ solution, exchange for 8 hours, rinse and filter with deionized water until neutral, repeat this 7 times; finally dry the resin rinsed to neutral at 70°C 8h, obtain exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1000° C. at a heating rate of 5° C./min, keep it warm for 80 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under _N2 atmosphere, the temperature was raised to 1000°C at a heating rate of 5°C/min, held for 80 minutes, and then lowered to room temperature at a cooling rate of 5°C/min to obtain sublimed deposited carbon with metallic luster.

Example 5

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 600rpm), 10g of cation exchange resin (macroporous strongly acidic styrene-based cation exchange resin D001) was pretreated with 0.75M HCl (500mL) for 18h;

(2) Rinse and filter the cationic resin pretreated in step (1) with deionized water until neutral, and dry at 75° C. for 8 hours;

(3) Add 300mL Ni(NO ₃ ) ₂ solution (0.075M concentration) into the dried cation exchange resin in step (2), under N ₂ atmosphere and stirring (stirring speed is 600rpm), Exchange for 8 hours, rinse and filter with deionized water until neutral; then add the same amount of Ni(NO ₃ ) ₂ solution, exchange for 8 hours, rinse and filter with deionized water until neutral, repeat this 7 times; finally rinse to The neutral resin was dried at 70°C for 8 hours to obtain the exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1000° C. at a heating rate of 5° C./min, keep it warm for 80 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under _N2 atmosphere, the temperature was raised to 1000°C at a heating rate of 5°C/min, held for 80 minutes, and then lowered to room temperature at a cooling rate of 5°C/min to obtain sublimed deposited carbon with metallic luster.

Example 6

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 800rpm), 15g of cation exchange resin (macroporous strongly acidic styrene-based cation exchange resin D001) was pretreated with 1M HCl (500mL) for 18h;

(2) Rinse and filter the cationic resin pretreated in step (1) with deionized water until neutral, and dry at 70° C. for 8 hours;

(3) Add 500mL Co(NO ₃ ) ₂ solution (concentration: 0.075M) into the dried cation exchange resin in step (2), under N ₂ atmosphere and stirring (stirring speed is 600rpm), Exchange for 8 hours, rinse and filter with deionized water until neutral; then add the same amount of Co(NO ₃ ) ₂ solution, exchange for 8 hours, rinse and filter with deionized water until neutral, repeat this 7 times; finally rinse to The neutral resin was dried at 80°C for 7 hours to obtain the exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1000° C. at a heating rate of 5° C./min, keep it warm for 80 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under _N2 atmosphere, the temperature was raised to 1000°C at a heating rate of 5°C/min, held for 80 minutes, and then lowered to room temperature at a cooling rate of 5°C/min to obtain sublimed deposited carbon with metallic luster.

Example 7

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 500rpm), 10g of anion exchange resin (strongly basic styrene-based anion exchange resin 201×7) was pretreated with 0.75M KOH (500mL) for 16h;

(2) Rinse and suction-filter the anion resin pretreated in step (1) with deionized water to neutrality, and dry at 70° C. for 8 hours;

(3) 300mL K ₃ [Fe(CN) ₆ ] solution (concentration is 0.075M) is added in the anion exchange resin through drying in step (2), under N ₂ Atmosphere and stirring (stirring speed is 600rpm) Under the conditions, exchange for 8 hours, rinse and filter with deionized water until neutral; then add the same amount of K ₃ [Fe(CN) ₆ ] solution, exchange for 8 hours, rinse and filter with deionized water until neutral, and repeat for 7 times; finally, the resin rinsed to neutral was dried at 70°C for 8 hours to obtain the exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and raise the temperature to 1000° C. at a heating rate of 10° C./min under _N atmosphere, keep it warm for 100 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under _N2 atmosphere, the temperature was raised to 1000°C at a heating rate of 5°C/min, held for 80 minutes, and then lowered to room temperature at a cooling rate of 5°C/min to obtain sublimed deposited carbon with metallic luster.

Example 8

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 500rpm), 20g of anion exchange resin (strongly basic styrene-based anion exchange resin 201×7) was pretreated with 0.5M KOH (800mL) for 24h;

(2) Rinse and suction-filter the anion resin pretreated in step (1) with deionized water to neutrality, and dry at 80° C. for 10 h;

(3) 300mL K ₄ [Fe(CN) ₆ ] solution (concentration is 0.075M) is added in the anion exchange resin through drying in step (2), under N ₂ Atmosphere and stirring (stirring speed is 600rpm) Under the conditions, exchange for 8 hours, rinse and filter with deionized water until neutral; then add the same amount of K ₄ [Fe(CN) ₆ ] solution, exchange for 8 hours, rinse and filter with deionized water until neutral, and repeat for 8 times; finally, the resin rinsed to neutral was dried at 70°C for 8 hours to obtain the exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1100° C. at a heating rate of 5° C./min, keep it warm for 60 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under N ₂ atmosphere, the temperature was raised to 1100 °C at a heating rate of 5 °C/min, kept for 80 min, and then lowered to room temperature at a cooling rate of 5 °C/min to obtain sublimed deposited carbon with metallic luster.

Example 9

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 700rpm), 10g of anion exchange resin (macroporous weakly basic styrene-based anion exchange resin D301) was pretreated with 0.5M KOH (1000mL) for 22h;

(2) Rinse and suction-filter the anion resin pretreated in step (1) with deionized water to neutrality, and dry at 70° C. for 8 hours;

(3) 300mL K ₃ [Fe(CN) ₆ ] solution (concentration is 0.1M) is added in the anion exchange resin through drying in step (2), under N ₂ Atmosphere and stirring (stirring speed is 600rpm) Under the conditions, exchange for 7 hours, rinse with deionized water and filter to neutral; then add the same amount of K ₃ [Fe(CN) ₆ ] solution, exchange for 7 hours, rinse with deionized water and filter to neutral, repeat this for 8 times; finally, the resin rinsed to neutral was dried at 70°C for 8 hours to obtain the exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1000° C. at a heating rate of 5° C./min, keep it warm for 80 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under _N2 atmosphere, the temperature was raised to 1000°C at a heating rate of 5°C/min, held for 80 minutes, and then lowered to room temperature at a cooling rate of 5°C/min to obtain sublimed deposited carbon with metallic luster.

Example 10

A sublimation deposited carbon with metallic luster, prepared by the following preparation method:

(1) Under the condition of mechanical stirring (stirring speed is 600rpm), 10g of anion exchange resin (macroporous weakly basic styrene-based anion exchange resin D301) was pretreated with 0.75M KOH (500mL) for 18h;

(2) Rinse and suction-filter the anion resin pretreated in step (1) with deionized water to neutrality, and dry at 70° C. for 10 h;

(3) 300mL K ₄ [Fe(CN) ₆ ] solution (concentration is 0.1M) is added in step (2) in the anion exchange resin through drying, under N ₂ atmosphere and stirring (stirring speed is 600rpm) Under the conditions, exchange for 9 hours, rinse and filter with deionized water until neutral; then add the same amount of K ₄ [Fe(CN) ₆ ] solution, exchange for 9 hours, rinse and filter with deionized water until neutral, and repeat for 6 times; finally, the resin rinsed to neutral was dried at 70°C for 8 hours to obtain the exchange resin;

(4) Put 8 g of the exchange resin in step (3) into a quartz porcelain boat, put it into a tube furnace, and under _N atmosphere, heat up to 1000° C. at a heating rate of 5° C./min, keep it warm for 80 minutes, and then heat it up for 5 minutes. The cooling rate of ℃/min is lowered to room temperature to obtain carbon powder;

(5) 0.8g of the carbon powder in step (4) is ball milled for 2 hours, then the ball milled carbon powder is mixed with glycine (the mass ratio of carbon powder: glycine is 1:8), put into a tube furnace, and Under N ₂ atmosphere, the temperature was raised to 1000 °C at a heating rate of 2 °C/min, kept for 60 min, and then lowered to room temperature at a cooling rate of 2 °C/min to obtain sublimed deposited carbon with metallic luster.

The performance test conditions of sublimation deposited carbon in fuel cells and lithium-ion batteries are:

The test of the sublimation deposited carbon with metallic luster prepared in Example 1 in a fuel cell: the fuel cell oxygen reduction reaction performance test adopts a three-electrode system, the working electrode is a glassy carbon rotating disk electrode, and the sublimation deposited carbon is made of slurry The form is dropped onto the surface of the rotating electrode and tested after drying sufficiently. The reference electrode is a silver/silver chloride electrode, and the counter electrode is a platinum sheet. The test is carried out in 0.1M KOH solution, the temperature is 25 degrees, and the American PINE bipotentiostat is used for testing. The potential range is -0.7V to 0.2V, the scanning speed is 10 millivolts per second, and the electrode speed is 400-2500rpm.

The sublimated deposited carbon with metallic luster prepared in Example 1 was tested for lithium batteries: the sublimed deposited carbon was used as the negative electrode material, made into a slurry and coated on the surface of copper foil, and after drying, it was packaged in a 2032 battery with a separator and a lithium sheet counter electrode in the shell. Using the Newwell lithium battery test system, charge and discharge at a current density of 100 mA per gram, and cycle up to 160 times. The cyclic voltammetry measurement of the battery is carried out on the Kester electrochemical workstation, using a three-electrode system, sublimated deposited carbon as the working electrode, the reference electrode and the counter electrode are both lithium sheets, the scanning range is 0-3 volts, and the scanning speed is 0.5 milliseconds. Ann per second.

The above-mentioned examples are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited by the above-mentioned examples, and any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention , all should be equivalent replacement methods, and are all included in the protection scope of the present invention.

Claims (10)

1. a preparation method of sublimation deposited carbon with metallic luster, is characterized in that: specifically comprise the following steps: (1) select ion exchange resin, carry out pretreatment to ion exchange resin; (2) rinsing the pretreated ion exchange resin in step (1) to neutrality and drying; (3) Add the metal salt solution to the dried ion exchange resin in step (2), exchange for 5-15 hours under _N2 atmosphere and stirring, rinse and filter until neutral; then add the metal salt solution , exchanged for 5-15 hours, rinsed and filtered until neutral, and repeated 5-10 times; finally, the resin rinsed to neutral was dried at 60-80°C for 6-12 hours to obtain an exchange resin; (4) Put the exchange resin in step (3) into a tube furnace, and in _N2 atmosphere, heat up to 900-1100°C at a heating rate of 2-10°C/min, keep it warm for 30-120min, and then heat it up at a rate of 2-10°C/min. The cooling rate of 10°C/min is lowered to room temperature to obtain carbon powder; (5) Ball-mill the carbon powder in step (4), then mix the ball-milled carbon powder with glycine, put it into a tube furnace, and raise the temperature at a heating rate of 2-10°C/min under _N2 atmosphere to 900-1100°C, keep warm for 30-120 minutes, and then drop to room temperature at a cooling rate of 2-10°C/min to obtain sublimed deposited carbon with metallic luster. 2. The method for preparing sublimation deposited carbon with metallic luster according to claim 1, characterized in that: the ion exchange resin described in step (1) is a cation exchange resin or an anion exchange resin. 3. according to claim 2, there is the preparation method of the sublimation deposition carbon of metallic luster, it is characterized in that: described cation exchange resin is strongly acidic styrenic cation exchange resin, weakly acidic styrenic cation exchange resin, macroporous Strongly acidic styrenic cation exchange resin or macroporous weakly acidic styrenic cation exchange resin. 4. according to claim 2, there is the preparation method of the sublimation deposition carbon of metallic luster, it is characterized in that: described anion exchange resin is strongly basic styrenic anion exchange resin, weakly basic styrenic anion exchange resin, large Porous strongly basic styrenic anion exchange resin or macroporous weakly basic styrenic anion exchange resin. 5. according to claim 1, there is the preparation method of the sublimation deposition carbon of metallic luster, it is characterized in that: the pretreatment described in step (1) is divided into the pretreatment of cation exchange resin and the pretreatment of anion exchange resin; The pretreatment method of the cation exchange resin is to pretreat 5 to 20 g of the cation exchange resin with 50 to 1000 mL of acid solution for 12 to 24 hours under stirring conditions; the concentration of the acid solution is 0.5 to 1 M; the acid solution It is HCl solution; the rotation speed of the stirring is 200～1000rpm; The pretreatment method of the anion exchange resin is: under the condition of stirring, pretreat 5-20g of anion exchange resin with 50-1000mL alkali solution for 12-24h; the concentration of the alkali solution is 0.5-1M; the alkali The solution is KOH solution or NaOH solution; the stirring speed is 200-1000rpm. 6. The method for preparing sublimation deposited carbon with metallic luster according to claim 1, characterized in that: the concentration of the metal salt solution in step (3) is 0.05-0.15M, and the metal salt solution and ion exchange resin The dosage ratio is (100-500) mL: (5-20) g. 7. according to claim 1, there is the preparation method of the sublimation deposition carbon of metallic luster, it is characterized in that: when ion exchange resin described in step (3) is cationic exchange resin, described metal salt solution is FeCl ₂ solution, FeCl ₃ solution, Ni(NO ₃ ) ₂ solution, NiCl ₂ solution, CoCl ₂ solution or Co(NO ₃ ) ₂ solution; when the ion exchange resin is an anion exchange resin, the metal salt solution is K One or more of ₃ [Fe(CN) ₆ ] solution or K ₄ [Fe(CN) ₆ ] solution. 8. The method for preparing sublimation deposited carbon with metallic luster according to claim 1, characterized in that: the rinsing in step (2) uses deionized water for rinsing; the drying condition is to dry at 60-80° C. ~12h; The stirring speed described in step (3) is 400～800rpm; The described rinsing adopts deionized water to rinse; The ball milling time in step (5) is 1-3 hours; the mass ratio of carbon powder to glycine is 1:(6-12). 9. A sublimation deposited carbon with metallic luster is prepared by the preparation method described in any one of claims 1-8. 10. The application of the sublimation deposited carbon with metallic luster according to claim 9, characterized in that: the application of the sublimated deposited carbon with metallic luster in fuel cell catalyst carrier, lithium ion battery negative electrode material and supercapacitor electrode material .