CN104157859A - Method for preparing high-performance lithium ion battery anode material with bagasse as raw material - Google Patents
Method for preparing high-performance lithium ion battery anode material with bagasse as raw material Download PDFInfo
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- CN104157859A CN104157859A CN201410429234.8A CN201410429234A CN104157859A CN 104157859 A CN104157859 A CN 104157859A CN 201410429234 A CN201410429234 A CN 201410429234A CN 104157859 A CN104157859 A CN 104157859A
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- bagasse
- ion battery
- lithium ion
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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
- H01M4/5835—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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention relates to the technical field of preparation of electrode materials of a lithium ion battery and particularly discloses a method for preparing a high-performance lithium ion battery anode material with bagasse as a raw material. The method includes following steps: washing the bagasse in deionized water, performing suction filtration and a drying process; performing calcination in an inert atmosphere; and carrying out a ball milling and sieving process to obtain the high-performance lithium ion battery anode material. The method is abundant in raw material source and is simple in processes. The prepared anode material is high in a reversible capacity and is excellent in a high-rate-circulation performance.
Description
Technical field
The present invention relates to the preparing technical field of lithium ion battery electrode material, be specifically related to a kind ofly take bagasse and prepare the method for high performance lithium ionic cell cathode material as raw material.
Background technology
Lithium ion battery, as a kind of novel high-energy battery, is widely used in daily life.Negative material is as the chief component of lithium electricity, and the quality of its performance directly affects the performance of lithium electricity.Graphite is as the most widely used carbon back lithium cell negative pole material at present, and its highest theoretical specific capacity is only 372mAhg
-1, actual specific capacity is lower, and cyclical stability is difficult to effective raising.Although the content of graphite of China is abundant, if do not protected, to be consumed totally sooner or later.Finding suitable new carbon-based material and replace current commercial negative material and promote battery capacity, raising cycle performance of battery, is the focus of current research.
The sugarcane acreage of China is only second to Brazil and India, occupies third place in the world, has the sugarcane of tens million of tons to be consumed every year, and the output of bagasse also reaches millions of tons.But owing to using development technique to fall behind, traditionally bagasse often go out of use need not, practical efficiency is very low, has not only caused the waste of resource, has also brought the pollution of environment.The main component of bagasse is cellulose, lignin, mainly containing elements such as C, O, Si, through carbonization treatment, forms and take carbon back as main, and the composite material that comprises Si oxide, applicable exploitation becomes new carbon-based composite electrode material.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of new lithium ion battery negative material, for the preparation of high-performance commercial Li-ion battery negative material provides a new approach.Being contemplated that of the inventive method: first bagasse is put into deionized water and carry out cleaned by ultrasonic vibration processing, suction filtration post-drying.Then under inert atmosphere conditions, calcine, with the cooled just sample of stove, after ball milling screening, obtain lithium ion battery negative material sample.Raw material sources of the present invention are abundant, and preparation technology is simple, and the negative material reversible capacity of preparing is high, high rate cyclic excellent performance.
Object of the present invention is specifically achieved by the following technical programs.
The bagasse of take is prepared the method for high performance lithium ionic cell cathode material as raw material, and step is as follows:
(1) bagasse is put into deionized water and carried out cleaned by ultrasonic vibration processing, after suction filtration, put into 60～100 ℃ of baking ovens and dry.
Described bagasse derives from fruit sugarcane and/or sugarcane.
(2) bagasse after drying is put into the reacting furnace of fixed bed reactors, under inert atmosphere, from room temperature, be warming up to 800～1000 ℃, and keep 2 hours, obtain lithium ion battery negative material head product after cooling.
Described inert atmosphere conditions is nitrogen or argon gas atmosphere.
The speed of described intensification is 5 ℃/min.
(3) by head product ball-milling treatment 2 hours (ball milling speed is 250 r/min) in ball mill, cross after 200 mesh sieves, obtain described lithium ion battery negative material.
Compared with prior art, the advantage of the inventive method and beneficial effect are:
The invention provides and a kind ofly take bagasse and prepare the new method of high performance lithium ionic cell cathode material as raw material, the method is first put into deionized water by bagasse and is carried out ultrasonic purification processing, after oven dry, under inert atmosphere conditions, calcine, with obtaining lithium ion battery negative material after the cooled head product ball milling screening of stove.The present invention compares with lithium ion battery negative material prepared by the additive method of bibliographical information, there are raw material sources abundant (Chinese bagasse annual output millions of tons), (raw material is Sugarcane By-product) with low cost, preparation technology's simple (only needing a step carbonization treatment), environmental protection (comprehensive utilization of bagasse), the negative material of preparing has the advantages such as reversible capacity is high, multiplying power cycle performance excellence with business negative material graphite-phase ratio.
Accompanying drawing explanation
Fig. 1 is process sonic oscillation clean, the fruit bagasse photo after suction filtration is dried.
Fig. 2 is the lithium ion battery negative material SEM figure of embodiment 1 preparation.
Fig. 3 is the lithium ion battery negative material SEM figure of embodiment 2 preparations.
Fig. 4 is the lithium ion battery negative material SEM figure of embodiment 3 preparations.
Fig. 5 is the CV curve chart of the lithium ion battery negative material of embodiment 3 preparations.
Fig. 6 is the lithium ion battery negative material of the embodiment 3 preparation discharge curve under 100mA/g condition.
Fig. 7 is the discharge-rate performance map of the lithium ion battery negative material of embodiment 3 preparations.
Fig. 2,3,4 results show, after carbonization treatment, sample major part presents laminated structure, also have block structure to occur simultaneously.Fig. 5 is the CV curve chart in first three week of sample of embodiment 3 preparations, occurs obvious redox peak in figure.Fig. 6 result shows, the sample of embodiment 3 preparations has higher capacity and cyclical stability under 100mA/g condition, and the 40 weeks later discharge capacities that circulates are 531mAh/g.Fig. 7 result shows, the sample high rate performance excellence of embodiment 3 preparations.Under different discharge-rate conditions, final specific discharge capacity is respectively 480mAh/g (100mA/g), 435mAh/g (200mA/g), 403mAh/g (500mA/g), 358mAh/g (1A/g), 310mAh/g (2A/g).The discharge capacity of electrode material reduces along with the increase of discharge-rate, but under each multiplying power condition, there is not obviously decay in discharge capacity, after 50 ladder multiplying power circulations, when current density comes back to 100mA/g, the discharge capacity of electrode material does not only reduce, and increases on the contrary 515mAh/g, and capability retention is 107%.
Embodiment
Applicant is described in further detail the inventive method in connection with specific embodiment below, and object is to make those skilled in the art can be expressly understood the present invention.Following examples should not be understood to the claims in the present invention book to ask for protection the restriction of scope in any degree.Those skilled in the art revise the similar electrode material of preparation by the application's thinking also should be in the claims in the present invention book be asked for protection the restriction of scope.
Embodiment 1
The bagasse of take is prepared the method for lithium ion battery negative material as raw material, and its step is as follows:
The daily accessory substance fruit bagasse that eats fruit sugarcane is put into deionized water, first stir 30 minutes, then sonic oscillation 1 hour, after suction filtration, fruit bagasse is put into 60 ℃ of baking ovens by its oven dry.Fruit bagasse after oven dry is put into the reacting furnace of fixed bed reactors, is warming up to 800 ℃ (heating rate is 5 ℃/min), and is incubated 2 hours under nitrogen atmosphere from room temperature at 800 ℃, obtains head product after cooling with stove.By head product ball-milling treatment 2 hours (ball milling speed 250r/min) in ball mill, cross after 200 mesh sieves, obtain lithium ion battery negative material (seeing Fig. 2).
Embodiment 2
The bagasse of take is prepared the method for lithium ion battery negative material as raw material, and its step is as follows:
Sugar refinery sugarcane is put into deionized water through remaining bagasse after squeezing sugar, first stir 30 minutes, then sonic oscillation 1 hour, after suction filtration, bagasse is put into 80 ℃ of baking ovens by its oven dry.Bagasse after oven dry is put into the reacting furnace of fixed bed reactors, is warming up to 900 ℃ (heating rate is 5 ℃/min), and is incubated 2 hours under argon gas atmosphere from room temperature at 900 ℃, obtains head product after cooling with stove.By head product ball-milling treatment 2 hours (ball milling speed 250r/min) in ball mill, cross after 200 mesh sieves, obtain lithium ion battery negative material (seeing Fig. 3).
Embodiment 3
The bagasse of take is prepared the method for lithium ion battery negative material as raw material, and its step is as follows:
The daily accessory substance fruit bagasse that eats fruit sugarcane is put into deionized water, first stir 30 minutes, then sonic oscillation 1 hour, after suction filtration, fruit bagasse is put into 100 ℃ of baking ovens by its oven dry.Fruit bagasse after oven dry is put into the reacting furnace of fixed bed reactors, is warming up to 1000 ℃ (heating rate is 5 ℃/min), and is incubated 2 hours under nitrogen atmosphere from room temperature at 1000 ℃, obtains head product after cooling with stove.By head product ball-milling treatment 2 hours (ball milling speed 250r/min) in ball mill, cross after 200 mesh sieves, obtain lithium ion battery negative material (seeing Fig. 4).
The lithium ion battery negative material that embodiment 1～3 is made is made half-cell and is carried out chemical property mensuration, and half-cell assembly method is as follows:
By testing sample, Super P Li conductive black and polyvinylidene fluoride (A Kema Kynoar binding agent HSV900 type), be 80wt%:15wt%:5wt% mixing in mass ratio, with 1-METHYLPYRROLIDONE, mix well, stir into thick, be coated on Copper Foil, at 80 ℃, vacuum (0.1MPa) dry 20 hours, be cut into the circular film of diameter 1cm after cooling.Half-cell adopts the assembling of CR2016 type button cell in glove box, and barrier film is Celgard 2400 polypropylene diaphragms, and electrolyte is 1M LiPF
6ethylene carbonate (EC) (in mixed electrolytic solution, the volume ratio of EC, DEC is 1:1, LiPF in mixed electrolytic solution with diethyl carbonate (DEC) mixed electrolytic solution
6concentration is 1M), negative pole is the circular lithium sheet (diameter 1.5cm) of commercialization, electrochemical property test carries out on the electric CT2001A type of indigo plant battery test system (production of Wuhan City Lan electricity electronics limited company).
In the CV curve chart of first three of battery week, there is obvious redox peak.Under 100mA/g condition, have higher capacity and cyclical stability, after circulating 40 weeks, discharge capacity is 531mAh/g.Under different discharge-rate conditions, final specific discharge capacity is respectively 480mAh/g (100mA/g), 435mAh/g (200mA/g), 403mAh/g (500mA/g), 358mAh/g (1A/g), 310mAh/g (2A/g).The discharge capacity of electrode material reduces along with the increase of discharge-rate, but under each multiplying power condition, there is not obviously decay in discharge capacity, after 50 ladder multiplying power circulations, when current density comes back to 100mA/g, the discharge capacity of electrode material does not only reduce, and increases on the contrary 515mAh/g, and capability retention is 107%.
Claims (4)
1. the bagasse of take is prepared the method for high performance lithium ionic cell cathode material as raw material, and step is as follows:
(1) bagasse is put into deionized water and carried out cleaned by ultrasonic vibration processing, after suction filtration, put into 60～100 ℃ of baking ovens and dry;
(2) bagasse after drying is put into the reacting furnace of fixed bed reactors, under inert atmosphere, from room temperature, be warming up to 800 ~ 1000 ℃, and keep 2 hours, obtain lithium ion battery negative material head product after cooling;
(3) by head product ball-milling treatment 2 hours in ball mill, cross after 200 mesh sieves, obtain described lithium ion battery negative material.
2. preparation method according to claim 1, is characterized in that: described bagasse derives from fruit sugarcane and/or sugarcane.
3. preparation method according to claim 1, is characterized in that: described inert atmosphere conditions is nitrogen or argon gas atmosphere.
4. preparation method according to claim 1, is characterized in that: the speed of described intensification is 5 ℃/min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106185862A (en) * | 2016-06-30 | 2016-12-07 | 中国科学院物理研究所 | A kind of pyrolyzed hard carbon material and application thereof |
| CN108059144A (en) * | 2017-12-11 | 2018-05-22 | 桂林电子科技大学 | Hard carbon prepared by a kind of biomass waste material bagasse and its preparation method and application |
| CN108439363A (en) * | 2018-02-26 | 2018-08-24 | 北京理工大学 | Sodium-ion battery hard carbon cathode material based on biomass |
| CN108862238A (en) * | 2018-09-06 | 2018-11-23 | 天津工业大学 | A kind of biomass waste material Shell of Water Chestnut base hard charcoal and its preparation method and application |
| CN111977649A (en) * | 2020-07-05 | 2020-11-24 | 桂林理工大学 | N, P codoped bagasse sheet-shaped mesoporous carbon lithium ion battery cathode material and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN1152372A (en) * | 1995-03-06 | 1997-06-18 | 索尼公司 | Negative electrode material for secondary cell for nonaqueous electrolytic solution, process for the production thereof, and secondary cell for nonaqueous electrolytic solution using it |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN103950916A (en) * | 2014-04-24 | 2014-07-30 | 合肥国轩高科动力能源股份公司 | Preparation method of carbonaceous anode material for lithium ion batteries |
-
2014
- 2014-08-27 CN CN201410429234.8A patent/CN104157859B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1152372A (en) * | 1995-03-06 | 1997-06-18 | 索尼公司 | Negative electrode material for secondary cell for nonaqueous electrolytic solution, process for the production thereof, and secondary cell for nonaqueous electrolytic solution using it |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN103950916A (en) * | 2014-04-24 | 2014-07-30 | 合肥国轩高科动力能源股份公司 | Preparation method of carbonaceous anode material for lithium ion batteries |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106185862A (en) * | 2016-06-30 | 2016-12-07 | 中国科学院物理研究所 | A kind of pyrolyzed hard carbon material and application thereof |
| CN106185862B (en) * | 2016-06-30 | 2018-09-11 | 中国科学院物理研究所 | A kind of pyrolyzed hard carbon material and application thereof |
| CN108059144A (en) * | 2017-12-11 | 2018-05-22 | 桂林电子科技大学 | Hard carbon prepared by a kind of biomass waste material bagasse and its preparation method and application |
| CN108439363A (en) * | 2018-02-26 | 2018-08-24 | 北京理工大学 | Sodium-ion battery hard carbon cathode material based on biomass |
| CN108439363B (en) * | 2018-02-26 | 2021-06-11 | 北京理工大学 | Biomass-based sodium ion battery |
| CN108862238A (en) * | 2018-09-06 | 2018-11-23 | 天津工业大学 | A kind of biomass waste material Shell of Water Chestnut base hard charcoal and its preparation method and application |
| CN111977649A (en) * | 2020-07-05 | 2020-11-24 | 桂林理工大学 | N, P codoped bagasse sheet-shaped mesoporous carbon lithium ion battery cathode material and preparation method thereof |
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| CN104157859B (en) | 2016-08-17 |
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Effective date of registration: 20230118 Address after: 1402, kuangu building, No.68, zone 2, Shiao village, Xinshi community, Dalang street, Longhua District, Shenzhen City, Guangdong Province 518000 Patentee after: Shenzhen Yizhuoer Energy Co.,Ltd. Address before: 432000 No. 272 traffic Avenue, Hubei, Xiaogan Patentee before: HUBEI ENGINEERING University |