CN105161681A - Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof - Google Patents

Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof Download PDF

Info

Publication number
CN105161681A
CN105161681A CN201510484495.4A CN201510484495A CN105161681A CN 105161681 A CN105161681 A CN 105161681A CN 201510484495 A CN201510484495 A CN 201510484495A CN 105161681 A CN105161681 A CN 105161681A
Authority
CN
China
Prior art keywords
carbon
carbon fluoride
coated
fluoride
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510484495.4A
Other languages
Chinese (zh)
Inventor
潘勇
朱岭
雷维新
周洁
李磊
马增胜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangtan University
Original Assignee
Xiangtan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangtan University filed Critical Xiangtan University
Priority to CN201510484495.4A priority Critical patent/CN105161681A/en
Publication of CN105161681A publication Critical patent/CN105161681A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof

Abstract

The invention discloses a microencapsulated carbon-coated carbon fluoride positive electrode material and a preparation method thereof, wherein the positive electrode material is formed by coating a layer of carbon on the surface of carbon fluoride particles; the preparation method comprises the steps of coating a layer of organic matter on the surfaces of carbon fluoride particles by using microcapsule technologies such as an interfacial polymerization method, a complex coacervation method and the like to prepare carbon fluoride microcapsule particles, and preparing the carbon-coated carbon fluoride anode material by using a high-temperature carbonization or concentrated sulfuric acid carbonization process. The carbon-coated carbon fluoride anode material prepared by the method has uniform particles and good conductivity, can avoid agglomeration among the particles, can improve the discharge voltage of the battery, and can improve the rate discharge performance.

Description

Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof
Technical Field
The invention relates to a preparation method of a microencapsulated carbon-coated carbon fluoride anode material, belonging to the field of battery anode materials, in particular to primary battery anode materials.
Background
In recent decades, with the rapid development of electronic information technology, batteries, which are one of the important power sources, have better performance requirements. The application of the primary battery in the fields of military, advanced medical treatment, aerospace and the like is also increasing and decreasing. At present, the most commonly used primary batteries comprise lithium-manganese dioxide batteries and alkaline zinc-manganese dioxide batteries, and the theoretical specific capacity of a manganese dioxide positive electrode material is only 308mAhg -1 It can only last 3 years when applied to a cardiac pacemaker. The theoretical specific capacity of the carbon fluoride anode material can reach 865mAhg -1 The material is a primary battery anode material with the highest theoretical specific capacity at present, has the advantages of environmental protection, no pollution, high safety, wide temperature range (-30-80 ℃), stable working voltage and the like, and is a hotspot of research in recent years.
However, the lithium fluorocarbon cell has poor conductivity, which causes serious polarization, low voltage platform and low discharge power, and affects the current application range of the lithium fluorocarbon cell. To this end, researchers have attempted a number of ways to improve the performance of fluorinated carbons. Zhang et al used a method of thermally decomposing polyvinylidene fluoride (PVDF) to coat CFx with carbon to increase its conductivity, and the prepared lithium fluorocarbon battery has an increased voltage and improved rate discharge performance. However, the carbon-coated carbon fluoride prepared by the method has the defects that particles are easy to agglomerate, the specific surface area is reduced, and the power density and the active substance utilization rate of the electrode material are influenced.
The invention provides a microencapsulated carbon-coated carbon fluoride anode material and a preparation method thereof. The carbon-coated carbon fluoride anode material which is not easy to agglomerate is prepared, and the conductivity and the specific surface area of the material are improved, so that the voltage platform and the rate discharge performance of the battery can be improved.
Disclosure of Invention
The invention aims to provide a carbon-coated carbon fluoride positive electrode material which is good in conductivity, large in specific surface area and not easy to agglomerate and a preparation method thereof.
The invention provides a carbon-coated carbon fluoride anode material which structurally comprises a layer of carbon coated on the surface of carbon fluoride.
The carbon-coated carbon fluoride cathode material also comprises the following preferred scheme:
the thickness of the carbon coating layer in the carbon-coated carbon fluoride cathode material is preferably 0.01-1.0 μm.
The carbon fluoride particles in the preferred carbon-coated carbon fluoride cathode material are one or more of carbon fluoride coke, graphite fluoride, graphene fluoride, carbon fluoride fibers and carbon fluoride nanotube particle materials.
The carbon-coated carbon fluoride cathode material preferably has carbon fluoride particles with a particle size distribution of 2 to 20 μm and a fluorine-to-carbon ratio of 0.8 to 1.2.
The invention also provides a preparation method of the microencapsulated carbon-coated carbon fluoride cathode material, which comprises the steps of coating a layer of organic matter on the surface of carbon fluoride particles by adopting a microcapsule technology to prepare carbon fluoride microcapsule particles, and then carbonizing the organic matter coated on the surface to obtain the carbon fluoride microcapsule particles.
The preparation method of the carbon-coated carbon fluoride cathode material further comprises the following preferred scheme:
the microcapsule technology in the preferred preparation method is one of an interfacial polymerization method, a complex agglomeration method, a single agglomeration method, an in-situ polymerization method and a spray drying method.
The carbonization process in the preferred preparation method is high-temperature pyrolysis carbonization or concentrated sulfuric acid carbonization.
In the preferred preparation method, the organic matter layer coated on the surface is one or more of carbohydrate, polyurea, polyurethane, resin, rubber, gelatin and Arabic gum.
The preparation method of the microencapsulated carbon-coated carbon fluoride cathode material comprises the following specific steps:
step 1: microencapsulation method for coating a layer of organic matter on the surface of carbon fluoride
The microcapsule particles coated with carbon fluoride are prepared by coating the surface of carbon fluoride with one or more of organic substances such as carbohydrate, polyurea, polyurethane, resin, rubber, gelatin, arabic gum and the like by adopting one of microcapsule coating technologies such as an interfacial polymerization method, a complex agglomeration method, a single agglomeration method, an in-situ polymerization method, a spray drying method and the like.
And 2, step: organic matter layer on surface of carbonized carbon fluoride microcapsule
And (3) carbonizing the organic matter coated on the surface of the carbon fluoride microcapsule prepared in the step (1) by adopting a high-temperature pyrolysis carbonization or concentrated sulfuric acid carbonization method to obtain the carbon-coated carbon fluoride anode material.
The invention has the beneficial effects that: the invention adopts the microencapsulation method to prepare the carbon-coated carbon fluoride anode material for the first time, and the prepared anode material has excellent conductivity, is not easy to agglomerate, has large specific surface area and can be used for preparing the lithium carbon fluoride battery with high capacity and high power. The technical scheme of the invention has the outstanding advantages that: 1. according to the invention, the surface of the carbon fluoride is coated with a layer of carbon, so that the conductivity can be improved, the electronic transmission is facilitated, the electrode polarization is slowed down, and the discharge voltage platform of the battery is improved; 2. the carbon-coated carbon fluoride prepared by the method based on the microcapsule technology has the characteristics of difficult agglomeration and large specific surface area, thereby increasing the active area of electrode reaction and improving the discharge power of the battery. 3. The preparation process is simple and easy to realize stable batch production.
Drawings
FIG. 1 is a flow chart and a schematic structural diagram of the preparation of a microencapsulated carbon-coated fluorocarbon positive electrode material. 1-carbon fluoride; 2-an organic substance; 3-carbon.
FIG. 2 is a scanning electron microscope image of the microencapsulated carbon-coated carbon fluoride material obtained in example 1.
Fig. 3 is a constant current discharge curve diagram of the battery made of the microencapsulated carbon-coated fluorocarbon positive electrode material and the raw fluorocarbon positive electrode material obtained in example 1. (a) is the discharge curve of raw fluorinated graphite; and (b) is the discharge curve of the carbon-coated graphite fluoride.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the invention.
Example 1
Taking graphite fluoride with the fluorine-carbon ratio of 1.0, wherein the particle size is 5-10 mu m, and carrying out microencapsulated carbon coating on the graphite fluoride by adopting an interface polymerization method, wherein the specific process comprises the following steps:
coating a layer of polyurea on the surface of the carbon fluoride by an interfacial polymerization method, and the specific process comprises the following steps:
(1) Mixing
0.1g of surfactant alkylphenol polyoxyethylene ether (OP-10) was added to 100mL of distilled water, and the mixture was stirred with a glass rod. Then, 2g of graphite fluoride was added thereto, and the mixture was stirred until it was uniformly mixed.
(2) Emulsification
2g of isophorone diisocyanate (IPDI) is weighed into the solution in step (1), and stirred for 15min with a high-speed stirrer at 2000rpm to form an oil/water mixed phase emulsion.
(3) Polymerisation
And (3) putting the solution in the step (2) into a constant-temperature water bath at 40 ℃, stirring at 500rpm, adding 0.05g of dibutyltin dilaurate (DBTDL) serving as a catalyst, and reacting for 8 hours.
(4) Filtering and drying
And (4) filtering the product obtained in the step (3), taking solid filter residues, washing the solid filter residues, and drying the solid filter residues in a vacuum drying oven at the temperature of 60 ℃ for 10 hours. The polyurea coated graphite fluoride microcapsule is obtained.
Carbonizing polyurea layer on carbon fluoride surface by concentrated sulfuric acid
Placing the prepared microcapsule of polyurea coated graphite fluoride in concentrated sulfuric acid with the mass fraction of 98%, and magnetically stirring for 12 hours; diluting concentrated sulfuric acid, filtering the powder, washing to neutrality, and drying. The polyurea-based microencapsulated carbon-coated graphite fluoride cathode material is prepared, and the scanning electron micrograph thereof is shown in FIG. 2.
Uniformly stirring the prepared microencapsulated carbon-coated graphite fluoride positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 7 6 The electrolyte solvent is 1.
The battery assembled in example 1 and a battery using carbon-uncoated graphite fluoride as a positive electrode under the same conditions were subjected to discharge test and comparison, and the discharge rate 1C was 865mAg -1 The average voltage was a voltage value at half the discharge capacity, and the results are shown in table 1 and fig. 3. As can be seen from the test results, example 1 carbon-coated graphite fluoride (CF) x C) Biortho fluorspar (CF) x ) The discharge plateau is improved, and the maximum discharge rate is improved to 5C from 0.5C before coating.
TABLE 1
Example 2
Taking the graphite fluoride with the fluorine-carbon ratio of 1.0, and the particle size is 5-10 mu m.
Firstly, coating a layer of Arabic gum-gelatin on the surface of carbon fluoride by a complex coacervation method, and the specific process comprises the following steps:
(1) Preparing solution
Adding 1g of gelatin and 1g of Arabic gum into 100mL of distilled water, adding 0.1g of OP-10 of surfactant and 0.1g of polyvinyl alcohol (PVA) as surfactant, stirring uniformly, and adjusting the pH value to 8.0; then 4g of carbon fluoride is added into the solution and stirred until the mixture is uniformly mixed.
(2) Emulsification
And (2) putting the solution prepared in the step (1) into a constant-temperature water bath at 50 ℃, and stirring for 15min at 600rpm to form a micro-emulsion.
(3) Crosslinking and curing
Gradually adjusting the pH of the solution obtained in the step (2) to 4.7 within 30min by using an acetic acid solution with the mass fraction of 5%, and reacting for 1h; then the temperature is reduced to 5 ℃, and 10ml of glutaraldehyde solution with the mass fraction of 10 percent is added -1 And reacting for 1h.
(4) Re-solidification of
Adding distilled water with 2 times of the volume of the solution in the step (3) for dilution, and using Na with the mass fraction of 10 percent 2 CO 3 Adjusting the pH value of the solution to 9; then the temperature is raised to 50 ℃ and kept for 70min.
(5) Washing and separating
And (4) reducing the temperature of the solution in the step (4) to 25 ℃, stirring for 12h, centrifuging and washing. Drying in a vacuum drying oven at 60 deg.C for 8 hr. The microcapsule of Arabic gum-gelatin coated carbon fluoride is prepared.
High-temperature carbonization Arabic gum-gelatin layer
And (3) putting the prepared Arabic gum-gelatin coated graphite fluoride microcapsule into an oven at 350 ℃ under the argon protection atmosphere for heat preservation for 3h for carbonization. The carbon-coated graphite fluoride cathode material is obtained.
Uniformly stirring the prepared carbon-coated graphite fluoride positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) in a mass ratio of 7 6 The electrolyte solvents are 1.
The assembled battery of example 2 was compared with a battery using graphite fluoride as a positive electrode not coated with carbon under the same conditions for a discharge test, and the test results are shown in table 2. As can be seen from the test results, example 2 carbon-coated graphite fluoride (CF) x C) Biortho fluorspar (CF) x ) The discharge plateau is improved, and the maximum discharge rate is improved to 5C from 0.5C before coating.
TABLE 2
。

Claims (4)

1. A microencapsulated carbon-coated carbon fluoride cathode material and a preparation method thereof are characterized in that the microencapsulated carbon-coated carbon fluoride cathode material is formed by coating a layer of carbon on the surface of carbon fluoride particles; the preparation method comprises the steps of coating a layer of organic matter on the surfaces of the carbon fluoride particles by adopting a microcapsule technology to prepare carbon fluoride microcapsule particles, and then carbonizing the organic matter coated on the surfaces of the carbon fluoride microcapsule particles to obtain the carbon fluoride microcapsule particles.
2. The microencapsulation technique of claim 1 wherein the method is one of interfacial polymerization, complex coacervation, simple coacervation, in situ polymerization, and spray drying. One of the interfacial polymerization method, the double agglomeration method and the spray drying method is preferable.
3. Carbonization according to claim 1, characterized by high-temperature pyrolysis carbonization or concentrated sulfuric acid carbonization.
4. The organic substance of claim 1, which is one of a carbohydrate, polyurea, polyurethane, resin, rubber, gelatin and gum arabic.
CN201510484495.4A 2015-08-10 2015-08-10 Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof Pending CN105161681A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510484495.4A CN105161681A (en) 2015-08-10 2015-08-10 Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510484495.4A CN105161681A (en) 2015-08-10 2015-08-10 Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN105161681A true CN105161681A (en) 2015-12-16

Family

ID=54802489

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510484495.4A Pending CN105161681A (en) 2015-08-10 2015-08-10 Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105161681A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107482187A (en) * 2017-07-27 2017-12-15 天津巴莫科技股份有限公司 Pitch carbon coating fluorocarbons positive electrode and preparation method thereof
CN107919465A (en) * 2017-11-01 2018-04-17 山东理工大学 A kind of phenolic resin base carbon coating fluorographite positive electrode and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1691374A (en) * 2004-04-29 2005-11-02 宁波杉杉新材料科技有限公司 Method for preparing artificial graphite cathode material of lithium ion battery
CN102091576A (en) * 2009-12-14 2011-06-15 武侯区巅峰机电科技研发中心 Controlled-stirring-speed microcapsule preparation process
CN102091577A (en) * 2009-12-14 2011-06-15 武侯区巅峰机电科技研发中心 Microcapsule preparation process capable of controlling core material to core wall ratio

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1691374A (en) * 2004-04-29 2005-11-02 宁波杉杉新材料科技有限公司 Method for preparing artificial graphite cathode material of lithium ion battery
CN102091576A (en) * 2009-12-14 2011-06-15 武侯区巅峰机电科技研发中心 Controlled-stirring-speed microcapsule preparation process
CN102091577A (en) * 2009-12-14 2011-06-15 武侯区巅峰机电科技研发中心 Microcapsule preparation process capable of controlling core material to core wall ratio

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Q. ZHANG等: ""Carbon-coated fluorinated graphite for high energy and high power densities primary lithium batteries"", 《JOURNAL OF POWER SOURCES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107482187A (en) * 2017-07-27 2017-12-15 天津巴莫科技股份有限公司 Pitch carbon coating fluorocarbons positive electrode and preparation method thereof
CN107482187B (en) * 2017-07-27 2020-07-03 天津巴莫科技股份有限公司 Asphalt carbon-coated carbon fluoride anode material and preparation method thereof
CN107919465A (en) * 2017-11-01 2018-04-17 山东理工大学 A kind of phenolic resin base carbon coating fluorographite positive electrode and preparation method thereof

Similar Documents

Publication Publication Date Title
CN107814382B (en) Long-life modified natural graphite negative electrode material and preparation method and application thereof
CN112225194B (en) Hard carbon material and preparation method and application thereof
CN107248569B (en) Antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as carbon source and preparation method and application thereof
CN110098391B (en) MXene-derived titanium dioxide/carbon-coated nano-silicon ternary composite material and preparation method thereof
CN106410177B (en) A kind of elliposoidal SiOx/ graphite cathode composite materials and its preparation method and application
CN108400297B (en) Silicon-based lithium ion battery cathode material and preparation method thereof
CN113629249B (en) Preparation method of MXene-based supported platinum catalyst applied to lithium-sulfur battery anode
CN111276677B (en) Preparation method of carbon nano material/amorphous carbon/silicon monoxide composite material
CN100383037C (en) Carbon material and nano silicon composite materials and method for preparing same and use thereof
CN109148865B (en) Preparation method of hard carbon composite carbon microsphere negative electrode material of lithium or sodium ion battery
CN111834612A (en) Hard carbon-silicon carbon composite material, preparation method thereof and lithium ion battery
CN113620272A (en) Preparation method of sodium ion battery negative electrode material
CN107482188B (en) Hollow core-shell structure composite material and preparation method and application thereof
CN113782718B (en) High-voltage lithium ion battery material, lithium ion battery and preparation method thereof
CN115010109A (en) Preparation method of novolac epoxy resin-based hard carbon material, hard carbon material and sodium ion battery
CN105185959A (en) Preparation method of carbon-coated carbon fluoride cathode material based on polyurea
CN105161681A (en) Microencapsulated carbon-coated carbon fluoride cathode material and preparation method thereof
CN113644244A (en) Chromium oxide/carbon fluoride/highly conductive substance composite material for lithium primary battery
CN110690423B (en) Heteroatom doped carbon material and preparation method and application thereof
CN110021744B (en) Preparation method of nano niobium dioxide/carbon lithium ion battery cathode material
CN114430038A (en) Fast-charging hard carbon negative electrode material and preparation method and application thereof
CN109273272B (en) Preparation method of sulfur-doped carbon micro-tube, sulfur-doped carbon micro-tube and application of sulfur-doped carbon micro-tube
CN105140520A (en) Preparation method of carbon-coated carbon fluoride positive electrode material based on Arabic gum-gelatin
CN113903915A (en) Preparation method of graphene-coated porous lead oxide-lead sulfide composite material
CN105336928B (en) Preparation method and application of polypyrrole-coated carbon fluoride cathode material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20151216