CN107968205A - A kind of method of the modified fluorinated carbon positive electrode of chemical reduction method - Google Patents
A kind of method of the modified fluorinated carbon positive electrode of chemical reduction method Download PDFInfo
- Publication number
- CN107968205A CN107968205A CN201711272530.1A CN201711272530A CN107968205A CN 107968205 A CN107968205 A CN 107968205A CN 201711272530 A CN201711272530 A CN 201711272530A CN 107968205 A CN107968205 A CN 107968205A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- fluorinated carbon
- modified fluorinated
- carbon positive
- preparation
- 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
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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
-
- 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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
Abstract
The invention discloses a kind of preparation method of modified fluorinated carbon positive electrode, including following preparation process：（1）Choose raw material：Including fluorocarbons, chemical reducing agent, solvent；（2）It is prepared by modified fluorinated carbon positive electrode：Certain proportion after chemical reducing agent and solvent are mixed, carries out material fluorocarbons under condition of heating and stirring electronation processing certain time, resulting materials are the modified fluorinated carbon positive electrode in the present invention after cooling filtering.The present invention improves the electronic conductivity of material, making lithium fluorocarbon battery, internal resistance reduces, and polarization phenomena are reduced, and improves lithium fluorocarbon battery discharge initial voltage hysteresis and multiplying power discharging property in electric discharge using chemical reduction method processing fluorocarbons.
Description
Technical field
The present invention is to belong to lithium battery material technical field, especially a kind of modified fluorinated carbon positive electrode of chemical reduction method
Preparation method
Technical background：
Lithium primary battery have the characteristics that many excellent performances and, including high voltage, high-energy-density, operating temperature range it is broad,
Long storage life etc..Currently used lithium primary battery mainly includes lithium manganese dioxide cell, lithium thionyl chloride cell, lithium/fluorine
Change carbon battery and lithium-sulfur dioxide cell.Wherein lithium fluorocarbon is theoretical system more highest than energy, about 2180Whkg-1, and since its positive electrode fluorocarbons chemical and physical features is stablized so that battery has the high temperature that long storage life is become reconciled
Performance.Therefore, as lithium fluorocarbon battery important component solid fluorinated carbon material preparation and be modified to for people close
The hot spot of note.
Fluorocarbons is the change platform thing that fluorine is directly reacted and generated with carbon at high temperature.When fluorocarbons is as cell positive material
When, its relatively low electronic conductivity can cause battery polarization to increase, cause the internal resistance of cell to increase, influence electricity in battery discharge
Tank discharge performance, seriously restricts the use of lithium/fluorination carbon battery.
The content of the invention
The technical problem to be solved in the present invention is：A kind of preparation for the fluorocarbons positive electrode that chemical reduction method is modified is provided
Method, the modified fluorinated carbon material electrical conductivity is big, can be effectively improved lithium fluorocarbon battery discharge initial voltage hysteresis and again
Rate discharge performance.
The present invention is for the scheme taken of solution the deficiencies in the prior art：
A kind of method of the modified fluorinated carbon positive electrode of chemical reduction method, including following preparation process：（1）Choose raw material：Bag
Include fluorocarbons, chemical reducing agent, solvent；（2）It is prepared by modified fluorinated carbon positive electrode：By fluorocarbons, chemical reducing agent and solvent
After being mixed, electronation processing is carried out to material under condition of heating and stirring, modified fluorinated carbon is being obtained just after cooling filtering
Pole material.
The fluorocarbons is one kind in fluorographite, carbon fluoride nano-tube or fluorinated graphene material, or it is a kind of with
Upper mixing, its fluorine carbon ratio are 0.9~1.0.
The chemical reducing agent is sodium borohydride, one kind in hydrazine hydrate, ethylenediamine, ascorbic acid, methanol, ethylene glycol
Or more than one mixing.
The solvent is one or both of deionized water, absolute ethyl alcohol.
Fluorocarbons, chemical reducing agent and the absolute ethyl alcohol mass ratio be：1: 0.3:1~1:5:5.
The reaction temperature is 20 DEG C~60 DEG C.
The reaction time is 1h~8h.
The stir speed (S.S.) is the r/min of 100r/min~2000.
Beneficial effects of the present invention：Fluorocarbons is handled using chemical reduction method, the electronic conductivity of material is improved, makes lithium fluorine
Change carbon battery electric discharge when, internal resistance reduce, polarization phenomena reduce, improve lithium fluorocarbon battery discharge initial voltage hysteresis and
Multiplying power discharging property.Therefore, the present invention is capable of providing a kind of strong one-shot battery of large current discharging capability, has very big industry
And commercial value.
Brief description of the drawings
Figure compared with Fig. 1 is the battery 0.1C discharge curve performances of the invention prepared with undressed fluorinated carbon material；
Figure compared with Fig. 2 is the battery 1C discharge curve performances of the invention prepared with undressed fluorinated carbon material.
Embodiment
In order to further understand the content, features and effects of the present invention, with reference to specific embodiment, and coordinate attached
Fig. 1~2 describe in detail.
A kind of preparation method of modified fluorinated carbon positive electrode, including following preparation process：
（1）Choose raw material：Including fluorocarbons, chemical reducing agent, solvent；
（2）It is prepared by modified fluorinated carbon positive electrode：According to a certain percentage by fluorocarbons, chemical reducing agent, after solvent is mixed,
Material is carried out under condition of heating and stirring electronation processing certain time, resulting materials is in the present invention after cooling filtering
Modified fluorinated carbon positive electrode.
Embodiment 1
It is by mass ratio:1:1:2 fluorographite, chemical reducing agent and solvent carries out electronation processing, reaction temperature 25
DEG C, reaction time 4h, after treatment filtering is modified fluorinated carbon material prepared by the present invention.Choose prepared by the present invention
Fluorinated carbon material is bonded in coating on aluminium collector with conductive agent and cathode is made.The content 88% of fluorinated carbon material.The kind of conductive agent
Class can be conductive carbon black, carbon nanotubes, and the total content of conductive agent is 5%.The species of binding agent is butadiene-styrene rubber, carboxymethyl is fine
The plain sodium of dimension, content 7%, lithium fluorocarbon battery is assembled into by positive plate and metal lithium sheet pairing.
Embodiment 2
It is by mass ratio:1:1.2:3 fluorographite, chemical reducing agent and solvent carry out electronation processing, and reaction temperature is
25 DEG C, reaction time 4h, after treatment filtering is modified fluorinated carbon material prepared by the present invention.The present invention is chosen to prepare
Fluorinated carbon material and conductive agent be bonded in coating on aluminium collector cathode be made.The content 88% of fluorinated carbon material.Conductive agent
Species can be conductive carbon black, carbon nanotubes, and the total content of conductive agent is 5%.The species of binding agent is butadiene-styrene rubber, carboxymethyl
Sodium cellulosate, content 7%, lithium fluorocarbon battery is assembled into by positive plate and metal lithium sheet pairing.
Embodiment 3
It is by mass ratio: 1:1.2:3 fluorographite, chemical reducing agent and solvent carry out electronation processing, and reaction temperature is
50 DEG C, reaction time 4h, after treatment filtering is modified fluorinated carbon material prepared by the present invention.The present invention is chosen to prepare
Fluorinated carbon material and conductive agent be bonded in coating on aluminium collector cathode be made.The content 88% of fluorinated carbon material.Conductive agent
Species can be conductive carbon black, carbon nanotubes, and the total content of conductive agent is 5%.The species of binding agent is butadiene-styrene rubber, carboxymethyl
Sodium cellulosate, content 7%, lithium fluorocarbon battery is assembled into by positive plate and metal lithium sheet pairing.
Comparative example 1：Fluorinated graphite material and conductive agent are bonded in coating on aluminium collector cathode is made.Fluorinated carbon material
Content 88%.The species of conductive agent can be conductive carbon black, carbon nanotubes, and the total content of conductive agent is 5%.The species of binding agent
For butadiene-styrene rubber, sodium carboxymethylcellulose, content 7%, lithium fluorocarbon battery is assembled into by positive plate and metal lithium sheet pairing.
As shown in Figure 1, lithium fluorocarbon battery prepared by above-described embodiment and comparative example is subjected to 0.1C discharge tests respectively
Compare, relative to untreated fluorinated graphite material, material voltage delay of the present invention reduces about 0.42V, and 2 platform of embodiment
Voltage improves about 0.15V, the almost free of losses of material gram specific capacity.
As shown in Figure 1, lithium fluorocarbon battery prepared by above-described embodiment and comparative example is subjected to 1C discharge test ratios respectively
Compared with relative to the fluorinated graphite material for processing, material voltage delay of the present invention reduces about 0.44V, and 2 platform of embodiment electricity
Pressure improves about 0.18V, the almost free of losses of material gram specific capacity.
As can be seen that lithium fluorocarbon battery prepared by the fluorocarbons positive electrode prepared using the present invention from Fig. 1, Fig. 2
The initial voltage hysteresis of discharging be improved significantly, platform voltage has a part lifting, and to gram specific capacity of material almost without
Influence, arrived with the increasing of discharge-rate, improvement is more obvious.
Claims (8)
- A kind of 1. method of the modified fluorinated carbon positive electrode of chemical reduction method, it is characterised in that：Including following preparation process：（1）Choose raw material：Including fluorocarbons, chemical reducing agent, solvent；（2）It is prepared by modified fluorinated carbon positive electrode：By fluorocarbons, after chemical reducing agent and solvent are mixed, in heating stirring Under the conditions of to material carry out electronation processing, cooling filtering after obtain modified fluorinated carbon positive electrode.
- 2. the preparation method of modified fluorinated carbon positive electrode according to claim 1, it is characterised in that：The fluorocarbons For one or more mixing in fluorographite, carbon fluoride nano-tube or fluorinated graphene material, its fluorine carbon ratio is 0.9 ~1.0.
- 3. the preparation method of modified fluorinated carbon positive electrode according to claim 1, it is characterised in that：The chemistry is also Former agent is sodium borohydride, one or more kinds of mixing in hydrazine hydrate, ethylenediamine, ascorbic acid, methanol, ethylene glycol.
- 4. the preparation method of modified fluorinated carbon positive electrode according to claim 1, it is characterised in that：The solvent is One or both of deionized water, absolute ethyl alcohol.
- 5. the preparation method of modified fluorinated carbon positive electrode according to claim 1, it is characterised in that：The fluorination Carbon, chemical reducing agent and absolute ethyl alcohol mass ratio are：1: 0.3:1~1:5:5.
- 6. the preparation method of modified fluorinated carbon positive electrode according to claim 1, it is characterised in that：The reaction temperature Spend for 20 DEG C~60 DEG C.
- 7. the preparation method of modified fluorinated carbon positive electrode according to claim 1, it is characterised in that：During described reaction Between be 1h~8h.
- 8. the preparation method of modified fluorinated carbon positive electrode according to claim 1, it is characterised in that：The stirring speed Rate is the r/min of 100r/min~2000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272530.1A CN107968205A (en) | 2017-12-06 | 2017-12-06 | A kind of method of the modified fluorinated carbon positive electrode of chemical reduction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711272530.1A CN107968205A (en) | 2017-12-06 | 2017-12-06 | A kind of method of the modified fluorinated carbon positive electrode of chemical reduction method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107968205A true CN107968205A (en) | 2018-04-27 |
Family
ID=61998885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711272530.1A Pending CN107968205A (en) | 2017-12-06 | 2017-12-06 | A kind of method of the modified fluorinated carbon positive electrode of chemical reduction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107968205A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108928809A (en) * | 2017-05-22 | 2018-12-04 | 天津大学 | The fluorine carbon ratio of carbon fluoride nano-tube regulates and controls method |
| CN109546105A (en) * | 2018-10-31 | 2019-03-29 | 贵州梅岭电源有限公司 | A kind of power-type lithium fluorocarbon battery and its manufacturing method |
| CN109659515A (en) * | 2018-11-23 | 2019-04-19 | 贵州梅岭电源有限公司 | A kind of preparation method of the fluorination carbon electrode material of Ag C modification |
| CN111224197A (en) * | 2020-01-06 | 2020-06-02 | 贵州梅岭电源有限公司 | Lithium fluorocarbon-supercapacitor quick response composite battery |
| CN112038650A (en) * | 2020-07-28 | 2020-12-04 | 天津力神电池股份有限公司 | Flexible package lithium fluorocarbon primary battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5654762A (en) * | 1979-10-09 | 1981-05-14 | Yuasa Battery Co Ltd | Manufacture of nonaqueous-electrolyte battery |
| CN104577107A (en) * | 2013-10-14 | 2015-04-29 | 中国电子科技集团公司第十八研究所 | Surface finish method of carbon fluoride material |
| CN106159268A (en) * | 2016-09-21 | 2016-11-23 | 贵州梅岭电源有限公司 | A kind of preparation method of modified fluorinated carbon positive electrode |
| CN106229511A (en) * | 2016-10-13 | 2016-12-14 | 江苏超电新能源科技发展有限公司 | Surface modifying method of a kind of fluorinated carbon material and products thereof and application |
-
2017
- 2017-12-06 CN CN201711272530.1A patent/CN107968205A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5654762A (en) * | 1979-10-09 | 1981-05-14 | Yuasa Battery Co Ltd | Manufacture of nonaqueous-electrolyte battery |
| CN104577107A (en) * | 2013-10-14 | 2015-04-29 | 中国电子科技集团公司第十八研究所 | Surface finish method of carbon fluoride material |
| CN106159268A (en) * | 2016-09-21 | 2016-11-23 | 贵州梅岭电源有限公司 | A kind of preparation method of modified fluorinated carbon positive electrode |
| CN106229511A (en) * | 2016-10-13 | 2016-12-14 | 江苏超电新能源科技发展有限公司 | Surface modifying method of a kind of fluorinated carbon material and products thereof and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108928809A (en) * | 2017-05-22 | 2018-12-04 | 天津大学 | The fluorine carbon ratio of carbon fluoride nano-tube regulates and controls method |
| CN109546105A (en) * | 2018-10-31 | 2019-03-29 | 贵州梅岭电源有限公司 | A kind of power-type lithium fluorocarbon battery and its manufacturing method |
| CN109659515A (en) * | 2018-11-23 | 2019-04-19 | 贵州梅岭电源有限公司 | A kind of preparation method of the fluorination carbon electrode material of Ag C modification |
| CN111224197A (en) * | 2020-01-06 | 2020-06-02 | 贵州梅岭电源有限公司 | Lithium fluorocarbon-supercapacitor quick response composite battery |
| CN111224197B (en) * | 2020-01-06 | 2021-10-22 | 贵州梅岭电源有限公司 | Lithium fluorocarbon-supercapacitor quick response composite battery |
| CN112038650A (en) * | 2020-07-28 | 2020-12-04 | 天津力神电池股份有限公司 | Flexible package lithium fluorocarbon primary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107968205A (en) | A kind of method of the modified fluorinated carbon positive electrode of chemical reduction method | |
| CN101867037B (en) | Iron-phosphate-based lithium-ion battery positive plate and preparation method thereof | |
| CN110010863A (en) | A kind of method of lithium ion battery negative material prelithiation | |
| CN106159268A (en) | A kind of preparation method of modified fluorinated carbon positive electrode | |
| CN104993100A (en) | Preparation method of carbon nitride nanotube-modified high rate performance nickel-cobalt-manganese ternary positive material | |
| CN104300129A (en) | Battery, battery cathode, battery cathode material and preparation method thereof | |
| CN111193022B (en) | Preparation and application of modified ammonium trifluorooxotitanate for lithium ion battery | |
| CN114583176A (en) | Multifunctional novel conductive agent and application thereof in pre-lithiation composite positive electrode | |
| CN108878893B (en) | Modified current collector for negative electrode of quick-charging lithium ion battery and preparation method thereof | |
| WO2021254393A1 (en) | Method for recycling battery electrodes | |
| US20230138359A1 (en) | Method for composite delamination | |
| CN101630734B (en) | Method for preparing electrode slices by modified anode materials for lithium-ion batteries | |
| CN109037645B (en) | Method for preparing metal oxide @ chlorine-doped graphene lithium ion battery anode material in one step | |
| JP2001210318A (en) | Manufacturing method of negative electrode for nonaqueous electrolytic solution secondary battery | |
| CN105489900A (en) | Preparation method of current collector for lithium-ion battery | |
| CN109888403A (en) | A kind of production method of stacked sodium-ion battery | |
| CN115642292A (en) | Zero-strain all-solid-state lithium-aluminum battery | |
| CN111370642A (en) | Conductive coating material based on graphene quantum dots and derivatives thereof and application thereof | |
| CN110364720B (en) | Positive active material, positive pole piece and preparation method thereof | |
| CN114229807A (en) | Si @ SiOx-TiN/C composite negative electrode material, preparation method and lithium ion battery | |
| CN109052471B (en) | Method for preparing lithium vanadate porous film by electrostatic spraying and application | |
| CN111628153A (en) | Novel lithium ion battery cathode material and preparation method thereof | |
| JP2009224188A (en) | Method of manufacturing lithium-ion secondary battery and its positive electrode plate | |
| JP3418940B2 (en) | Method for producing negative electrode current collector for zinc alkaline battery | |
| CN109309223A (en) | A kind of Co3O4/ Pd nanometer combined electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180427 |
|
| RJ01 | Rejection of invention patent application after publication |