CN104882609A - Surface modification treatment method for negative electrode graphite in low-temperature lithium ion battery - Google Patents
Surface modification treatment method for negative electrode graphite in low-temperature lithium ion battery Download PDFInfo
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- CN104882609A CN104882609A CN201510185838.7A CN201510185838A CN104882609A CN 104882609 A CN104882609 A CN 104882609A CN 201510185838 A CN201510185838 A CN 201510185838A CN 104882609 A CN104882609 A CN 104882609A
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a surface modification treatment method for negative electrode graphite in a low-temperature lithium ion battery. The method comprises the following steps: adding graphite into concentrated sulfuric acid according to mass ratio, mixing and stirring for 10-50min, then adding potassium permanganate and accessory ingredients, oxidizing at temperature of 0-30 DEG C for 1-3h, then adding redistilled water and hydrogen peroxide, stirring for cooling, filtering, washing with water, taking out graphite, and performing high-temperature oxidation treatment on the graphite under conditions that the temperature is 400-600 DEG C and the oxidation treatment time is controlled within 10-50min; after oxidizing, soaking the graphite into a lithium carbonate solution for 1-5h; after soaking, washing with water until the pH is equal to 7; and finally performing vacuum drying on the graphite under a condition that the temperature is 120 DEG C. By virtue of vacuum drying, the negative positive graphite which is subjected to surface modification treatment and used for low-temperature lithium ion batteries can be prepared, not only can the defect degree of graphite be reduced, but also the irreversible capacity and ion diffusion speed of the graphite can be improved, the graphite interlayer spacing is enlarged, and the transmission rate and structural stability of the lithium ion battery are improved.
Description
Technical field
The invention belongs to technical field of lithium ion, specifically the surface modifying treatment of negative pole graphite in a kind of low-temperature lithium ion battery.
Technical field
Lithium ion battery has that specific energy is high, quality is light, the life-span is long and the advantage such as memory-less effect, is widely used in the field such as various consumer electronic device and electric automobile, energy storage, portable power source.Along with the raising that people require low-temperature lithium ion battery, especially in northern frore area or field, there is higher low temperature charging and discharging capabilities.
The graphite that in low-temperature lithium ion battery, negative material uses is one of principal element affecting its cryogenic property.
The main method of current raising negative material cryogenic property has:
1) graphite surface modification: to change the kind of graphite surface functional group, quantity and defect thereof, to increase compatibility and the structural stability of graphite and electrolyte;
2) increase graphite layers distance: with improve lithium ion in lithium ion charge and discharge process embedding go out speed and ion diffusion rates, improve the structural stability in course of reaction;
3) composite negative pole electrode is prepared: in graphite, namely add conductive agent or be mixed into loosely organized carbon foam to improve its conductance.
Only adopt a certain single method very limited to the cryogenic property effect improving negative material, such as at preparation and the Electrochemical Properties [Gao Jie thereof of low-temperature lithium ion battery negative material, in April, 2007] in a literary composition, although by adopting different method for coating at Graphite Coating layer of metal, amorphous carbon or oxide, so as to sheltering the active site of graphite surface, thus avoid the decomposition of PC, but stability and cycle performance poor, conductance increase rate is little, preparation process is complicated, be difficult to ensure consistency, cause Industry Promotion more difficult.
Improve the cryogenic property of negative material and to improve its imbibition liquid-keeping property be current main direction of studying.
Summary of the invention
For solving the problem, the invention provides the surface modifying treatment of negative pole graphite in a kind of low-temperature lithium ion battery, this surface modifying treatment changes the kind of functional group by liquid phase oxidation and adds the interlamellar spacing that auxiliary agent adds graphite, improve surface stability and the ion transportation of graphite, the graphite prepared not only has low temperature charging and discharging capabilities excellence, good cycle, feature that imbibition liquid-keeping property is strong, preparation method's technique is simple, and cost of manufacture is low.
For achieving the above object, the present invention adopts following technical scheme:
A surface modifying treatment for negative pole graphite in low-temperature lithium ion battery, this surface modifying treatment uses graphite, the concentrated sulfuric acid, potassium permanganate, auxiliary agent, redistilled water, hydrogen peroxide and lithium carbonate, and feature of the present invention is as follows:
By quality proportioning be: graphite: the concentrated sulfuric acid: potassium permanganate: auxiliary agent: redistilled water: hydrogen peroxide=1: { 6 ~ 8}: { 1.2 ~ 1.5}: { 0 ~ 2}: { 5 ~ 15}: { 2 ~ 6};
Above-mentioned auxiliary agent is any one in formic acid, acetic acid, iron chloride, nitric acid;
According to above-mentioned mass ratio, graphite is added to mix and blend 10 ~ 50min in the concentrated sulfuric acid, add potassium permanganate and auxiliary agent afterwards and be oxidized 1 ~ 3h when temperature 0 ~ 30 DEG C, add redistilled water and hydrogen peroxide again, through filtering after stirring cooling, wash graphite taking-up and carry out high temperature oxidation process under 400 ~ 600 DEG C of conditions, the time controling of oxidation processes is at 10 ~ 50min, again graphite is put into Lithium carbonate solution after oxidation and invade bubble 1 ~ 5h, invade bubble after washing to pH=7, finally graphite is carried out vacuum drying under 120 DEG C of conditions, vacuum drying can be prepared through surface modification treatment and for the negative pole graphite in low-temperature lithium ion battery,
The concentration of above-mentioned lithium carbonate controls at 0.4 ~ 0.6g/L;
The performance requirement of the negative pole graphite of effects on surface modification is as follows:
Gram volume>=370mAh/g, first efficiency>=94%, 0 DEG C of gram volume>=250mAh/g, interlamellar spacing D
002>=0.3490nm, diffusion coefficient>=1.0 × 10
-11.
Owing to adopting technical scheme described above, the present invention produces following good effect:
1, the present invention first adopts liquid phase surface modification can reduce the degree of imperfection of graphite, increase the pore quantity that graphite surface forms nanostructure, the increase of pore quantity had both added storage lithium position, improve irreversible capacity and the ion diffusion rates of graphite, adopt oxidant and auxiliary agent can increase the interlamellar spacing of graphite again, improve transmission rate and the structural stability of lithium ion battery.
2, the present invention use auxiliary agent belong to Small molecular class, this auxiliary agent as intercalator leading and embed graphite linings formed intercalation compound, improve the dilation of graphite; This auxiliary agent can play again and help oxidation agent, assists oxidant to be oxidized graphite, promotes that intercalation carries out, improves the low temperature charging and discharging capabilities of graphite.
3, the present invention adopts lithium carbonate to clean the lithium ion content that can supplement graphite surface, makes it effectively can reduce the consumption of lithium ion in electrolyte in lithium ion battery course of reaction, reduces the thickness of SEI film, thus reduces internal resistance and improve cycle performance.
Embodiment
The present invention is the surface modifying treatment of negative pole graphite in a kind of low-temperature lithium ion battery, this surface modifying treatment first adopts liquid phase surface modification can reduce the degree of imperfection of graphite, increase the pore quantity that graphite surface forms nanostructure, the increase of pore quantity had both added storage lithium position, improve irreversible capacity and the ion diffusion rates of graphite, adopt oxidant and auxiliary agent can increase the interlamellar spacing of graphite again, improve transmission rate and the structural stability of lithium ion battery, the auxiliary agent wherein used belongs to Small molecular class, this auxiliary agent is leading and embed graphite linings and form intercalation compound and can improve the dilation of graphite as intercalator, this auxiliary agent can play again and help oxidation agent, oxidant is assisted to be oxidized graphite, promote that intercalation carries out, improve the low temperature charging and discharging capabilities of graphite.
The preferred iron chloride of formic acid in auxiliary agent, acetic acid, iron chloride, nitric acid.
Three embodiments are for sketching content and following technical scheme of the present invention below; three embodiments can explain the present invention in more detail; the present invention is not limited to following examples, discloses object of the present invention and is intended to protect all changes and improvements in the scope of the invention.
Embodiment 1
Take 1.0 grams of graphite and add mix and blend 30min in 7.0 grams of concentrated sulfuric acids to, add 1.3 grams of potassium permanganate and 1.0 grams of iron chloride afterwards, and be 25 DEG C in temperature, after oxidation 2h, add 10 grams of redistilled waters and 3 grams of hydrogen peroxide, stir cooled and filtered, washing, by graphite in atmosphere temperature be carry out oxidation processes 30min under 500 DEG C of conditions, be cooled to room temperature afterwards, the Lithium carbonate solution of 0.5mol/L is adopted to soak 2h afterwards, be washed to neutrality again, 120 DEG C of vacuum dryings obtain modified graphite cathode material.
Embodiment 2
Take 1.0 grams of graphite and add mix and blend 10min in 6.0 grams of concentrated sulfuric acids to, add 1.2 grams of potassium permanganate and 0.1 gram of acetic acid afterwards, and be 0 DEG C in temperature, after oxidation 3h, add 5 grams of redistilled waters and 2 grams of hydrogen peroxide, stir cooled and filtered, washing, by graphite in atmosphere temperature be carry out oxidation processes 50min under 400 DEG C of conditions, be cooled to room temperature afterwards, the Lithium carbonate solution of 0.4mol/L is adopted to soak 5h afterwards, be washed to neutrality again, 120 DEG C of vacuum dryings obtain modified graphite cathode material.
Embodiment 2
Take 1.0 grams of graphite and add mix and blend 50min in 8.0 grams of concentrated sulfuric acids to, add 1.5 grams of potassium permanganate and 2.0 grams of nitric acid afterwards, and be 30 DEG C in temperature, after oxidation 1h, add 15 grams of redistilled waters and 6 grams of hydrogen peroxide, stir cooled and filtered, washing, by graphite in atmosphere temperature be carry out oxidation processes 10min under 600 DEG C of conditions, be cooled to room temperature afterwards, the Lithium carbonate solution of 0.6mol/L is adopted to soak 1h afterwards, be washed to neutrality again, 120 DEG C of vacuum dryings obtain modified graphite cathode material.
Potassium permanganate in above-described embodiment uses as oxidant.
Button electrical testing
Gained negative material in embodiment 1-3 is assembled into button cell A1, A2, A3, preparation method summary be: carry out stirring pulping add binding agent, conductive agent and solvent in negative material after and be coated on Copper Foil, drying, roll obtained.
Described binding agent is LA132 binding agent, and described conductive agent is SP, and described solvent is redistilled water, and concrete proportioning is: negative material: SP:LA132: redistilled water=95g:1g:4g:220mL;
The proportioning that electrolyte adopts is LiPF
6/ EC:DEC=1:1, metal lithium sheet is to electrode, barrier film adopts polythene PE, polypropylene PP or poly-second propylene PEP composite membrane, simulated battery is assemblied in the glove box filling hydrogen and carries out, chemical property carries out on the blue electric CT2001A type cell tester in Wuhan, charging/discharging voltage scope is 0.005 ~ 2.0V, and charge-discharge velocity is 0.1C.
Comparative example is with the Delanium that market is purchased for negative material, and button electrical test results sees the following form.
| Detain battery | A1 | A2 | A3 | Comparative example |
| Negative material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Delanium |
| Discharge capacity mAh/g first | 378.2 | 376.4 | 372.3 | 339.5 |
| Discharging efficiency % first | 94.1 | 94.3 | 93.1 | 91.4 |
| 0 DEG C of discharge capacity mAh/g | 252 | 249 | 239 | 188 |
As can be seen from the above table: adopt embodiment 1 ~ 3 to prepare its first charge-discharge capacity of negative material and efficiency apparently higher than comparative example, result shows to have higher discharge capacity and efficiency through the negative pole graphite of surface modification treatment, reason is reduce the degree of imperfection of negative pole graphite through peroxidating and therefore improve the gram volume of negative pole graphite, negative pole graphite simultaneously through surface modification treatment makes its interlamellar spacing and conductance be improved, thus low temperature discharge capacity is also improved.
Soft-package battery is tested
Respectively using embodiment 1-3 gained as negative material, take LiFePO4 as positive electrode, adopt volume ratio LiPF
6/ EC: DEC=1: 1 as electrolyte, and Celgard 2400 film is barrier film, prepares 5AH soft-package battery B1, B2, B3, and the cryogenic property of testing its negative material.
Comparative example is that soft-package battery test result sees the following form with the Delanium that market is purchased for negative material and the same 5AH soft-package battery B for preparing of other condition.
As can be seen from the above table, embodiment is improved significantly compared with the cryogenic property of comparative example, its reason is because negative material is reduced through surface oxidation and its degree of imperfection, interlamellar spacing obtains becoming large simultaneously, be conducive to lithium ion in lithium ion battery course of reaction embedding go out, thus improve the cryogenic property of lithium ion battery.
Claims (1)
1. the surface modifying treatment of negative pole graphite in low-temperature lithium ion battery, this surface modifying treatment uses graphite, the concentrated sulfuric acid, potassium permanganate, auxiliary agent, redistilled water, hydrogen peroxide and lithium carbonate, it is characterized in that:
By quality proportioning be: graphite: the concentrated sulfuric acid: potassium permanganate: auxiliary agent: redistilled water: hydrogen peroxide=1: { 6 ~ 8}: { 1.2 ~ 1.5}: { 0 ~ 2}: { 5 ~ 15}: { 2 ~ 6};
Above-mentioned auxiliary agent is any one in formic acid, acetic acid, iron chloride, nitric acid;
According to above-mentioned mass ratio, graphite is added to mix and blend 10 ~ 50min in the concentrated sulfuric acid, add potassium permanganate and auxiliary agent afterwards and be oxidized 1 ~ 3h when temperature 0 ~ 30 DEG C, add redistilled water and hydrogen peroxide again, through filtering after stirring cooling, wash graphite taking-up and carry out high temperature oxidation process under 400 ~ 600 DEG C of conditions, the time controling of oxidation processes is at 10 ~ 50min, again graphite is put into Lithium carbonate solution after oxidation and invade bubble 1 ~ 5h, invade bubble after washing to pH=7, finally graphite is carried out vacuum drying under 120 DEG C of conditions, vacuum drying can be prepared through surface modification treatment and for the negative pole graphite in low-temperature lithium ion battery,
The concentration of above-mentioned lithium carbonate controls at 0.4 ~ 0.6g/L;
The performance requirement of the negative pole graphite of effects on surface modification is as follows:
Gram volume>=370mAh/g, first efficiency>=94%, 0 DEG C of gram volume>=250mAh/g, interlamellar spacing D
002>=0.3490nm, diffusion coefficient>=1.0 × 10
-11.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510185838.7A CN104882609A (en) | 2015-04-20 | 2015-04-20 | Surface modification treatment method for negative electrode graphite in low-temperature lithium ion battery |
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| CN201510185838.7A CN104882609A (en) | 2015-04-20 | 2015-04-20 | Surface modification treatment method for negative electrode graphite in low-temperature lithium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109509873A (en) * | 2017-09-14 | 2019-03-22 | 丰田自动车株式会社 | The cathode graphite material and its manufacturing method of lithium ion secondary battery |
| CN112174129A (en) * | 2020-10-14 | 2021-01-05 | 宁波锋成先进能源材料研究院有限公司 | Liquid nitrogen assisted graphene oxide preparation method |
| CN112952069A (en) * | 2021-04-06 | 2021-06-11 | 黑龙江省宝泉岭农垦溢祥新能源材料有限公司 | Production process of carbon-coated graphite negative electrode material |
Citations (2)
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| JP2000053408A (en) * | 1998-08-05 | 2000-02-22 | Hitachi Chem Co Ltd | Expanded graphite particle, its production, lithium secondary cell, its negative pole and negative pole material |
| CN102701194A (en) * | 2012-06-19 | 2012-10-03 | 上海交通大学 | Method for processing graphite oxide |
-
2015
- 2015-04-20 CN CN201510185838.7A patent/CN104882609A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000053408A (en) * | 1998-08-05 | 2000-02-22 | Hitachi Chem Co Ltd | Expanded graphite particle, its production, lithium secondary cell, its negative pole and negative pole material |
| CN102701194A (en) * | 2012-06-19 | 2012-10-03 | 上海交通大学 | Method for processing graphite oxide |
Non-Patent Citations (2)
| Title |
|---|
| GUANGYU ZHAO等: "Enhanced low temperature performances of expanded commercial mesocarbon microbeads(MCMB) as lithium ion battery anodes", 《MATERIALS LETTERS》 * |
| 魏召唤: "低温锂离子电池石墨负极改性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109509873A (en) * | 2017-09-14 | 2019-03-22 | 丰田自动车株式会社 | The cathode graphite material and its manufacturing method of lithium ion secondary battery |
| CN109509873B (en) * | 2017-09-14 | 2022-03-11 | 丰田自动车株式会社 | Graphite material for negative electrode of lithium ion secondary battery and method for producing same |
| CN112174129A (en) * | 2020-10-14 | 2021-01-05 | 宁波锋成先进能源材料研究院有限公司 | Liquid nitrogen assisted graphene oxide preparation method |
| CN112952069A (en) * | 2021-04-06 | 2021-06-11 | 黑龙江省宝泉岭农垦溢祥新能源材料有限公司 | Production process of carbon-coated graphite negative electrode material |
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