CN102070137B - Preparation method of carbon foam with high electrochemical performances - Google Patents

Preparation method of carbon foam with high electrochemical performances Download PDF

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Publication number
CN102070137B
CN102070137B CN2010105985035A CN201010598503A CN102070137B CN 102070137 B CN102070137 B CN 102070137B CN 2010105985035 A CN2010105985035 A CN 2010105985035A CN 201010598503 A CN201010598503 A CN 201010598503A CN 102070137 B CN102070137 B CN 102070137B
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carbon foam
carbon
solvent
preparation
vanadate
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CN102070137A (en
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甘礼华
吕耀康
刘明贤
曹永杰
陈龙武
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Tongji University
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Tongji University
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Abstract

The invention relates to a preparation method of carbon foam with high electrochemical performances, comprising the following steps of: firstly, weighing phenol formaldehyde, vanadate, surface active agent, sodium hydroxide and solvent according to mass ratio of 1:(0.6-4):(0.01-0.5):(1-20):(0.01-0.5):100, mixing uniformly and obtaining precursor solution of the carbon foam; putting the obtained solution into an environment with the temperature of 15 DEG C-60 DEG C to lead the solvent to be completely volatilized, and obtaining precursor of solid carbon foam; and solidifying the precursor of the solid carbon foam for 1 hour-24 hours at the temperature of 100 DEG C-200 DEG C, then rising the temperature to be 600 DEG C-1400 DEG C at the temperature rising speed of 1 DEG C/min-60 DEG C/min under the inert atmosphere, carbonizing for 0.5 hour-10 hours, and obtaining the carbon foam with high electrochemical performances. In the preparation method, the technology is simple, the quality is stable, vanadate introduced when the precursor solution of the carbon foam is prepared is converted into sodium vanadate nanocrystalline with a stable layer structure in the process of carbonization, and the obtained sodium vanadate nanocrystalline is embedded into a carbon foam skeleton uniformly. Compared with the existing carbon foam, the prepared carbon foam has the electrochemical performances such as high mass specific capacitance, good charging and discharging circulation and the like, and can be effectively applied in the fields such as electrode materials of electrochemical capacitors and the like.

Description

The carbon foamy preparation method that a kind of chemical property is high
Technical field
The present invention relates to the high carbon foamy preparation method of a kind of chemical property, specifically is that the embedding vanadic acid sodium is nanocrystalline to improve carbon foam chemical property in the carbon foam framework.Carbon foamy chemical property with method preparation of the present invention is improved significantly.
Background technology
The carbon foam is a kind of solid-state material with cancellated low density, high porosity, high-specific surface area.At present both at home and abroad the carbon foam of report has higher specific surface area, and good erosion resistance, thermostability and snappiness, and characteristics such as high opening pore space structure are a kind of very rising electrode materialss.Denomination of invention is that " carbon foam and preparation method thereof " (Chinese invention patent, the patent No.: ZL 01816023.9) discloses a kind of carbon foamy preparation method, and has described this carbon foam is incorporated into various final application, comprises battery electrode, electrode for capacitors etc.; " store battery that comprises the carbon foam current collector " (Chinese invention patent, patent No.: ZL03814736.X) disclose a kind of preparation method who is used for the carbon foam current collector of store battery; " nonconductive carbon foam that is used for store battery " (Chinese invention patent application number: 200780050031.6; Publication number: CN101584063A) disclose a kind of carbon foam battery that electricity is used that is used for; Comprising nonconducting relatively low density, the carbon foamy preparation method of high porosity.But in these carbon foams; There are shortcomings such as specific conductivity is not high, surface carbon atom relative inertness mostly; Thereby make the carbon foam relatively poor to the wettability of electrolyte solution; Can not utilize its surface, duct to carry out charge storage fully, and cause carbon foamy chemical property not ideal enough thus, limit the carbon foamy and further used.Therefore, the research of the method for exploration raising carbon foam chemical property has practical significance.
Summary of the invention
The objective of the invention is to disclose a kind of carbon foamy preparation method; Carbon foam with method preparation of the present invention is good to the wettability of electrolyte solution; Can make full use of its surface, duct and carry out charge storage, therefore no matter as battery electrode, or electrode for capacitors; All can overcome the existing dissatisfactory shortcoming of chemical property that carbon foam specific conductivity is not high, surface carbon atom relative inertness causes; For the practical application of carbon foam in fields such as electrochemical capacitor electrode materials contributes, and steady quality, technology is simple.
In order to achieve the above object; The present invention has introduced vannadate in preparation carbon foam precursor solution; It is nanocrystalline that vannadate changes into the vanadic acid sodium with stable laminate structure in subsequent carbonization process; Embed in the carbon foam framework uniformly, thereby improved carbon foamy degree of graphitization, conductivity and wettability, obtain having the carbon foam of higher quality than electric capacity and favorable charge-discharge cycle performance.
Concrete preparation method carries out as follows:
Earlier take by weighing phenol: formaldehyde: vannadate: tensio-active agent: sodium hydroxide: solvent=1: (0.6～4): (0.01～0.5): (1～20): (0.01～0.5) by mass ratio: 100, mix, obtain carbon foam precursor solution.Then gained carbon foam precursor solution is placed 15～60 ℃ environment, solvent is wherein volatilized fully, obtain the solid carbon foam precursor.Then the solid carbon foam precursor with gained solidifies 1～24h down at 100～200 ℃, then under the protection of inert atmosphere, is warming up to 600～1400 ℃ of charing 0.5～10h with the temperature rise rate of 1～60 ℃/min, obtains the high carbon foam of chemical property.
Above-mentioned tensio-active agent can be polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer EO 20PO 70EO 20, or polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer EO 106PO 70EO 106, or sorbitan oleate.Vannadate can be a sodium metavanadate, or ammonium meta-vanadate.Solvent can be water, anhydrous methanol, absolute ethyl alcohol, THF, acetone, methyl-sulphoxide, N, a kind of in dinethylformamide or the dioxane.Inert atmosphere is nitrogen or argon gas.
Advantage of the present invention is:
1. owing to preparing at the carbon foamy, the present invention introduced vannadate in the process; It is nanocrystalline that vannadate changes into the vanadic acid sodium with stable laminate structure in carbonization process; Embed the carbon foam framework; Thereby improved carbon foamy degree of graphitization and conductivity, made the carbon foam have higher quality than electric capacity and favorable charge-discharge cycle performance.
2. the carbon foam that makes of the present invention is owing to exist vanadic acid sodium nanocrystalline in its skeleton; Improved carbon foamy wettability; Thereby help it as battery electrode; Or electrolytic solution can fully contact with the carbon foam electrode during electrode for capacitors, has increased the rate of migration of ion in carbon foam duct, thereby has improved carbon foamy chemical property.
3. the carbon foam that makes of the present invention is in the charge and discharge cycles process; The electric double layer capacitance and the nanocrystalline fake capacitance of vanadic acid sodium of carbon foam framework have been coupled; Therefore the carbon foam carbon foam nanocrystalline with not embedding vannadate that the present invention obtained compared, and quality improves than electric capacity.
4. in the carbon foam that the present invention makes; Vannadate is nanocrystalline not to be to load on carbon foamy outside surface; But embed equably in the carbon foamy skeleton, thereby the carbon foam both can be worked in neutral electrolyte solution, also can in strong alkaline electrolytes solution, work.
5. technology of the present invention is simple, and the carbon froth quality that makes is stable, and the carbon foam of the acquisition carbon foam nanocrystalline with not embedding vannadate compared, and quality improves 2～25% than electric capacity.
Embodiment
Embodiment 1
Press phenol: formaldehyde: sodium metavanadate: EO 20PO 70EO 20: sodium hydroxide: absolute ethyl alcohol=1: 1: 0.01: the ratio of 1: 0.01: 100 mass ratio takes by weighing, and obtains carbon foam precursor solution after mixing.The carbon foam precursor solution of gained is placed 15 ℃ environment, solvent is volatilized fully, obtain the solid carbon foam precursor.The solid carbon foam precursor of gained solidifies 24h at 100 ℃, and the temperature rise rate with 1 ℃/min is warming up to 600 ℃ of charing 10h under the protection of nitrogen atmosphere again, obtains the carbon foam.EO 20PO 70EO 20Be the SILVER REAGENT product of buying from U.S. Sigma-Aldrich company, other raw materials are commercially available.
Take by weighing above-mentioned carbon foam by mass ratio: the ptfe emulsion of 12wt% (buying): absolute ethyl alcohol=90: 10: 50 from Shanghai Sanaifu New Material Co., Ltd; After mixing; Ir lamp is oven dry down; The oven dry sample being pressed under the pressure of 10MPa on the nickel foam (buying from Liyuan New Material Co Ltd, Changsha), in 80 ℃ of vacuum-drying 24h, is made electrode slice.Be made into electrode with this electrode slice, in 7mol/L KOH solution, be assembled into electrochemical capacitor.
In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 3%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 10%.
Embodiment 2
Press phenol: formaldehyde: sodium metavanadate: EO 20PO 70EO 20: sodium hydroxide: absolute ethyl alcohol=1: 4: 0.03: the ratio of 2: 0.03: 100 mass ratio takes by weighing, and obtains carbon foam precursor solution after mixing.The carbon foam precursor solution of gained is placed 30 ℃ environment, make solvent evaporates, obtain the solid carbon foam precursor.The solid carbon foam precursor of gained solidifies 12h at 100 ℃, under the protection of nitrogen atmosphere, is warming up to 700 ℃ of charing 5h with the temperature rise rate of 30 ℃/min and obtains the carbon foam.
Press the method for embodiment 1, be made into electrode, in 7mol/LKOH solution, be assembled into electrochemical capacitor with this carbon foam.In current density is under the condition of 100mA/g, and the quality of this carbon foam is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 5%; In current density is under the condition of 3A/g, and the quality of this carbon foam is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 10%.
Embodiment 3
Press phenol: formaldehyde: sodium metavanadate: EO 106PO 70EO 106: sodium hydroxide: absolute ethyl alcohol=1: 0.6: 0.05: the ratio of 2: 0.05: 100 mass ratio takes by weighing, and obtains carbon foam precursor solution after mixing.The carbon foam precursor solution of gained is placed 30 ℃ environment, make solvent evaporates, obtain the solid carbon foam precursor.The solid carbon foam precursor of gained solidifies 12h at 100 ℃, under the protection of nitrogen atmosphere, is warming up to 950 ℃ of charing 3h with the temperature rise rate of 60 ℃/min and obtains the carbon foam.
EO 106PO 70EO 106Be the SILVER REAGENT product of buying from U.S. Sigma-Aldrich company, other raw materials are commercially available.
The electrode of using this carbon foam making by the method for embodiment 1 is assembled into electrochemical capacitor in 7mol/LKOH solution.In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 7%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 20%.
Embodiment 4
In phenol: formaldehyde: ammonium meta-vanadate: sorbitan oleate: sodium hydroxide: water=1: 2: 0.2: the ratio of 20: 0.2: 100 mass ratio takes by weighing, and obtains carbon foam precursor solution after mixing.The carbon foam precursor solution of gained is placed 60 ℃ environment, make solvent evaporates, obtain the solid carbon foam precursor.The solid carbon foam precursor of gained solidifies 6h at 150 ℃, under the protection of nitrogen atmosphere, is warming up to 1400 ℃ of charing 0.5h with the temperature rise rate of 10 ℃/min and obtains the carbon foam.
The electrode of using this carbon foam making by the method for embodiment 1 is assembled into electrochemical capacitor in 7mol/LKOH solution.In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 10%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 20%.
Embodiment 5
In phenol: formaldehyde: sodium metavanadate: sorbitan oleate: sodium hydroxide: methyl alcohol=1: 2: 0.5: the ratio of 20: 0.5: 100 mass ratio takes by weighing, and obtains carbon foam precursor solution after mixing.The carbon foam precursor solution of gained is placed 25 ℃ environment, make solvent evaporates, obtain the solid carbon foam precursor.The solid carbon foam precursor of gained solidifies 1h at 200 ℃, under the protection of argon atmospher, is warming up to 800 ℃ of charing 3.5h with the temperature rise rate of 5 ℃/min and obtains the carbon foam.
The electrode of using this carbon foam making by the method for embodiment 1 is assembled into electrochemical capacitor in 7mol/LKOH solution.In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 10%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 25%.
Embodiment 6
Solvent is a THF, and all the other are identical with embodiment 1, obtains carbon foam of the present invention.
The electrode of using this carbon foam making by the method for embodiment 1 is assembled into electrochemical capacitor in 7mol/LKOH solution.In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 3%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 10%.
Embodiment 7
Solvent is an acetone, and all the other are identical with embodiment 1, obtains carbon foam of the present invention.
The electrode of using this carbon foam making by the method for embodiment 1 is assembled into electrochemical capacitor in 7mol/LKOH solution.In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 2%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 5%.
Embodiment 8
Solvent is a methyl-sulphoxide, and all the other are identical with embodiment 1, obtains carbon foam of the present invention.
The electrode of using this carbon foam making by the method for embodiment 1 is assembled into electrochemical capacitor in 7mol/LKOH solution.In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 3%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 10%.
Embodiment 9
Solvent is N, dinethylformamide, and all the other are identical with embodiment 1, obtain carbon foam of the present invention.
The electrode of using this carbon foam making by the method for embodiment 1 is assembled into electrochemical capacitor in 7mol/LKOH solution.In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 4%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 10%.
Embodiment 10
Solvent is a dioxane, and all the other are identical with embodiment 1, obtains carbon foam of the present invention.
The electrode of using this carbon foam making by the method for embodiment 1 is assembled into electrochemical capacitor in 7mol/LKOH solution.In current density is under the condition of 100mA/g, and this carbon foamy quality is compared the carbon foam of not introducing vannadate than electric capacity and improved more than 4%; In current density is under the condition of 3A/g, and this carbon foamy quality is compared than electric capacity and do not embedded the nanocrystalline carbon foam of vanadic acid sodium and improved more than 10%.

Claims (1)

1. carbon foamy preparation method that chemical property is high is characterized in that:
Earlier take by weighing phenol: formaldehyde: vannadate: tensio-active agent: sodium hydroxide: solvent=1: (0.6～4): (0.01～0.5): (1～20): (0.01～0.5) by mass ratio: 100, mix, obtain carbon foam precursor solution; Carbon foam precursor solution with gained places 15～60 ℃ environment then, and solvent is wherein volatilized fully, obtains the solid carbon foam precursor; Then the solid carbon foam precursor with gained solidifies 1～24h down at 100～200 ℃, then under the protection of inert atmosphere, is warming up to 600～1400 ℃ of charing 0.5～10h with the temperature rise rate of 1～60 ℃/min, obtains the high carbon foam of chemical property;
Described tensio-active agent is polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer EO 20PO 70EO 20, or polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer EO 106PO 70EO 106, or sorbitan oleate;
Described vannadate is a sodium metavanadate, or ammonium meta-vanadate;
Described solvent is water, anhydrous methanol, absolute ethyl alcohol, THF, acetone, methyl-sulphoxide, N, a kind of in dinethylformamide or the dioxane;
Described inert atmosphere is a nitrogen, or argon gas.
CN2010105985035A 2010-12-21 2010-12-21 Preparation method of carbon foam with high electrochemical performances Expired - Fee Related CN102070137B (en)

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CN102553529B (en) * 2011-12-21 2013-08-14 同济大学 Preparation method for sulfur functionalization carbon foam
CN102745670B (en) * 2012-07-30 2014-10-08 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of three-dimensional ordered macroporous composite material
CN103325575B (en) * 2013-05-16 2016-07-06 陶荣燕 The chemical synthesizing method of high dielectric electrode paper tinsel
CN109205590B (en) * 2018-09-28 2022-03-11 陕西科技大学 Vanadium nitride nanocluster loaded on 3D carbon foam framework and preparation method thereof

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