CN105826522A - Method for preparing in-situ carbon coated manganese carbonate for negative electrode of lithium ion battery - Google Patents
Method for preparing in-situ carbon coated manganese carbonate for negative electrode of lithium ion battery Download PDFInfo
- Publication number
- CN105826522A CN105826522A CN201610333350.9A CN201610333350A CN105826522A CN 105826522 A CN105826522 A CN 105826522A CN 201610333350 A CN201610333350 A CN 201610333350A CN 105826522 A CN105826522 A CN 105826522A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- carbon
- manganese carbonate
- negative electrode
- solution
- 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.)
- Granted
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
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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 discloses a one-step method for in-situ preparation of carbon coated manganese carbonate for the negative electrode of a lithium ion battery .The method specifically comprises the steps of 1, preparing potassium permanganate solution of certain concentration and carbon source solution of certain concentration respectively, wherein the molar concentration ratio of the carbon source solution to the potassium permanganate solution is 1:(2-2.5); 2, adding the carbon source solution to the potassium permanganate solution, and conducting stirring dispersion and ultrasonic treatment in sequence; 3, adding dispersed solution into a reaction still to be heated for 3-24 h at the temperature of 120-180 DEG C; 4, naturally cooling the reaction still to room temperature, and conducting cleaning and drying to obtain powder, namely the in-situ carbon coated manganese carbonate for the negative electrode of a lithium ion battery .Raw materials for preparation are cheap and easy to obtain, operation is easy, energy consumption is low, pollution is avoided, carbon coating of the obtained manganese carbonate is uniform, size distribution is uniform, purity is high, particle collapse during charging and discharging of manganese carbonate can be effectively prevented, and the cycling stability of the lithium ion battery is improved.
Description
Technical field
The present invention relates to battery material technical field, be specifically related to the system of a kind of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate
Preparation Method.
Background technology
Along with the flourish of lithium ion battery is more wide with apply, its portability and energy density are proposed higher by market
Requirement.As the ingredient that lithium ion battery is important, negative material is most important on the impact of performance.But, existing
Commercialization negative material Carbon anode is difficult to meet such requirement, therefore through row research and changes various alternative type negative materials
Property be solve this problem important method.
At present, negative material can be divided into insert type, alloy-type and conversion type three class from from storage lithium mechanism.And conversion type negative pole phase
For alloy-type and insert type electrode, there is high power capacity, the advantages such as discharge and recharge change in volume is less, be therefore more suitable for the lithium in future
Electricity market.Transition metal carbonate using manganese carbonate as representative is as novel conversion type lithium ion battery negative material, from 2007
Obtain great concern since being reported for the first time in year, but be similar to other materials based on conversion reaction mechanism, manganese carbonate
Deng transition metal carbonate negative material, to equally exist in charge and discharge process change in volume big, and structural collapse, capacity declines, and enters
And cause lithium ion battery chemical property to be decayed, have a strong impact on the actual application in terms of lithium ion battery of this type of material.
To this end, how to overcome the disadvantages mentioned above of the transition metal carbonate negative materials such as manganese carbonate to become the most both at home and abroad by modified method
The emphasis of many scholar's research.At present, conventional modified method has carbon cladding, morphology control etc., but, these methods are often
Preparation process is loaded down with trivial details, preparation condition is harsh, energy consumption is high, and obtained product is unsatisfactory, is unfavorable for industrialization actual production.
Summary of the invention
The purpose of the present invention is contemplated to solve the problems referred to above, it is provided that a kind of one-step method prepares used as negative electrode of Li-ion battery carbon bag in situ
The method covering manganese carbonate, the method prepares cheaper starting materials and is easy to get, power consumption simple to operate less, pollution-free, obtained manganese carbonate carbon
Being evenly coated, even particle size distribution, purity is high, it is possible to effectively prevent granule collapse phenomenon in manganese carbonate charge and discharge process, improves
Lithium ion battery cyclical stability.
To achieve these goals, the present invention adopts the following technical scheme that
The preparation method of a kind of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate, comprises the following steps:
(1) the mole dense of certain density potassium permanganate solution and carbon source solution, described carbon source and potassium permanganate solution is prepared respectively
Degree ratio is 1:2-2.5；
(2) carbon source solution is joined in potassium permanganate solution, supersound process after dispersed with stirring；
(3) being joined by scattered solution in reactor and heat, heating-up temperature is 120 DEG C-180 DEG C, and heat time heating time is 3-24h；
(4) reactor naturally cools to room temperature, cleans, and dried gained powder body is used as negative electrode of Li-ion battery in-situ carbon cladding
Manganese carbonate.
Wherein the carbon source in step (1) includes one or more in glucose, sucrose and oxalic acid；
Preferably, in described step (1), carbon source is glucose；
Preferably, in described step (1), carbon source solution concentration is 0.02～0.1 mol/L；
Preferably, in described step (2), supersound process frequency is 15～22Hz, and the process time is 5～20 minutes；
Preferably, in described step (3), heating-up temperature is 180 DEG C, and heat time heating time is 6h.
The present invention also provides for a kind of used as negative electrode of Li-ion battery in-situ carbon cladding carbonic acid manganese material prepared according to said method.
Additionally, the present invention also provides for a kind of lithium ion battery negative, the material of described battery cathode is foregoing in-situ carbon bag
Cover manganese carbonate material.
Finally, the present invention also provides for a kind of lithium ion battery, and the negative material of described lithium ion battery is in-situ carbon bag as previously mentioned
Cover manganese carbonate material.
Beneficial effect:
Carbon source the most of the present invention primarily serves two kinds of effects in preparation process, on the one hand reacts generation manganese carbonate with potassium permanganate, separately
On the one hand carbon is evenly coated at the manganese carbonate surface formation complex of formation, and the existence of carbon source simultaneously the most effectively inhibits manganese carbonate brilliant
The reunion of body, therefore obtained carbon cladding manganese carbonate even particle size distribution, it is achieved one-step method prepares used as negative electrode of Li-ion battery in situ
Carbon cladding manganese carbonate, is greatly simplified preparation process, prepares material cheap and easy to get, and production cost is low, and beneficially industrialization is extensive
Produce；
Preparation method the most of the present invention power consumption is few, only reacts under relatively lower temp and i.e. can get final products, and product is located after being not required to
Reason, course of reaction Environmental Safety, produce without poisonous and harmful substance；
Gained manganese carbonate carbon the most of the present invention is evenly coated, and purity is high, it is possible to effectively prevent granule collapse in manganese carbonate charge and discharge process
Phenomenon, improves lithium ion battery cyclical stability.
Accompanying drawing explanation
Fig. 1 is the SEM figure of gained powder body in embodiment 1；
Fig. 2 is the TEM figure of gained powder body in embodiment 1；
Fig. 3 is the SEM figure of gained powder body in embodiment 2；
Fig. 4 is the TEM figure of gained powder body in embodiment 2.
Detailed description of the invention
The invention will be further described with embodiment below in conjunction with the accompanying drawings.Should be noted that the description below merely to explain
The present invention, is not defined its content.
Embodiment 1
(1) compound concentration is the potassium permanganate solution of 0.25 mol/L, dispersed with stirring；
(2) glucose solution of 0.1 mol/L, dispersed with stirring are prepared；
(3) joining in potassium permanganate solution by above-mentioned glucose solution, supersound process 22Hz after dispersed with stirring, during process
Between be 5 minutes；
(4) scattered solution is joined reactor is heated to 180 DEG C keep 6 hours；
(5) reactor heated naturally cools to room temperature, cleans, finally obtains powder body after drying.
Obtain the test result of powder body:
As shown in fig. 1, carbon cladding manganese carbonate crystal is the spindle bodily form to SEM pattern, and carbon layer on surface is uniformly coated with, crystal size
It is evenly distributed；TEM pattern is as in figure 2 it is shown, carbon cladding manganese carbonate crystal presents the spindle bodily form, it is evident that manganese carbonate crystal
Being made up of double-layer structure, wherein top layer is the carbon-coating of uniformly cladding and small manganese carbonate, and internal core is manganese carbonate granule.
Battery test system is used to test, in electric current density 100mAg obtaining spindle bodily form manganese carbonate-1At the beginning of condition obtains
Beginning capacity is 1180mAh/g, capacity stationary value 450mAh/g after circulating 100 weeks.Prove that it has good electrochemistry circulation
Stability.
Embodiment 2
(1) compound concentration is the potassium permanganate solution of 0.04 mol/L, dispersed with stirring；
(2) oxalic acid solution of 0.02 mol/L, dispersed with stirring are prepared；
(3) above-mentioned oxalic acid solution is joined in potassium permanganate solution, supersound process 15Hz after dispersed with stirring, process the time
It it is 20 minutes；
(4) scattered solution is joined reactor is heated to 120 DEG C keep 10 hours；
(5) reactor heated naturally cools to room temperature, cleans, finally obtains powder body after drying.
Obtain the test result of powder body:
As shown in Figure 3, carbon cladding manganese carbonate crystal is the square of regular shape to SEM pattern, and carbon layer on surface is uniformly coated with,
Lens capsule is uniform；As shown in Figure 4, carbon cladding manganese carbonate crystal presents and has the square of regular shape TEM pattern, can
Will become apparent from manganese carbonate crystal to be made up of double-layer structure, wherein top layer is carbon-coating and small manganese carbonate, the internal core of uniformly cladding
For manganese carbonate granule.
Use the battery test system square manganese carbonate test to obtaining, electric current density 100mAg-1Obtaining initial capacity is
998mAh/g, capacity stationary value 430mAh/g after circulating 100 weeks.Experiment proves that it has good electrochemical cycle stability.
Comparative example 1
Method, with embodiment 1, except for the difference that uses manganese sulfate to replace potassium permanganate, uses sodium bicarbonate to replace glucose.
Use the battery test system manganese carbonate test to obtaining, electric current density 100mAg-1Under the conditions of, obtaining initial capacity is
950mAh/g, capacity stationary value 230mAh/g after circulating 100 weeks.
It is not difficult to find out by comparative example 1, uses the manganese carbonate that manganese sulfate and sodium bicarbonate prepare, its initial capacity and capacity stationary value
Relatively the application the most significantly declines, and electrochemical cycle stability is poor.
Although the detailed description of the invention of the present invention is described by the above-mentioned accompanying drawing that combines, but not limit to scope
System, one of ordinary skill in the art should be understood that on the basis of technical scheme, and those skilled in the art need not pay
Go out various amendments or deformation that creative work can make still within protection scope of the present invention.
Claims (9)
1. a preparation method for used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate, comprises the following steps:
(1) the mole dense of certain density potassium permanganate solution and carbon source solution, described carbon source and potassium permanganate solution is prepared respectively
Degree ratio is 1:2-2.5；
(2) carbon source solution is joined in potassium permanganate solution, supersound process after dispersed with stirring；
(3) being joined by scattered solution in reactor and heat, heating-up temperature is 120 DEG C-180 DEG C, and heat time heating time is 3-24h；
(4) reactor naturally cools to room temperature, cleans, and dried gained powder body is used as negative electrode of Li-ion battery in-situ carbon cladding
Manganese carbonate.
The preparation method of a kind of used as negative electrode of Li-ion battery in-situ carbon the most as claimed in claim 1 cladding manganese carbonate, its feature exists
In, in described step (1), carbon source solution concentration is 0.02～0.1 mol/L.
The preparation method of a kind of used as negative electrode of Li-ion battery in-situ carbon the most as claimed in claim 1 cladding manganese carbonate, its feature exists
In, the carbon source in described step (1) includes one or more in glucose, sucrose and oxalic acid.
The preparation method of a kind of used as negative electrode of Li-ion battery in-situ carbon the most as claimed in claim 3 cladding manganese carbonate, its feature exists
In, in described step (1), carbon source is glucose.
The preparation method of a kind of used as negative electrode of Li-ion battery in-situ carbon the most as claimed in claim 1 cladding manganese carbonate, its feature exists
In, in described step (2), supersound process frequency is 15～22Hz, and the process time is 5～20 minutes.
The preparation method of a kind of used as negative electrode of Li-ion battery in-situ carbon the most as claimed in claim 1 cladding manganese carbonate, its feature exists
In, in described step (3), heating-up temperature is 180 DEG C, and heat time heating time is 6h.
7. a kind of used as negative electrode of Li-ion battery in-situ carbon carbon coated that the method as described in claim 1-6 any one prepares
Acid manganese material.
8. a lithium ion battery negative, it is characterised in that the material of described battery cathode is original position as claimed in claim 7
Carbon cladding carbonic acid manganese material.
9. a lithium ion battery, it is characterised in that the negative material of described lithium ion battery is the original position described in claim 7
Carbon cladding carbonic acid manganese material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610333350.9A CN105826522B (en) | 2016-05-18 | 2016-05-18 | A kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610333350.9A CN105826522B (en) | 2016-05-18 | 2016-05-18 | A kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105826522A true CN105826522A (en) | 2016-08-03 |
| CN105826522B CN105826522B (en) | 2018-02-02 |
Family
ID=56530723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610333350.9A Active CN105826522B (en) | 2016-05-18 | 2016-05-18 | A kind of preparation method of used as negative electrode of Li-ion battery in-situ carbon cladding manganese carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105826522B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784825A (en) * | 2017-03-15 | 2017-05-31 | 北京理工大学 | A kind of spherical nickeliferous carbonic acid manganese material and its preparation method and application |
| CN107910525A (en) * | 2017-11-16 | 2018-04-13 | 中山大学 | A kind of preparation method of N doping manganese carbonate and its compound |
| CN110504437A (en) * | 2019-08-30 | 2019-11-26 | 浙江大学山东工业技术研究院 | A kind of coated porous sodium manganate composite material and preparation method of polypyrrole and application |
| CN112661189A (en) * | 2020-12-25 | 2021-04-16 | 陕西科技大学 | Manganese carbonate nano material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN103500833A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Method for preparing lithium iron phosphate positive electrode material coated by home position graphitization carbon |
-
2016
- 2016-05-18 CN CN201610333350.9A patent/CN105826522B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN103500833A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Method for preparing lithium iron phosphate positive electrode material coated by home position graphitization carbon |
Non-Patent Citations (1)
| Title |
|---|
| LIANKAI ZHOU ET.AL.: "Hydrothermal Fabrication of MnCO3@rGO Composite as an Anode", 《INORGANIC CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784825A (en) * | 2017-03-15 | 2017-05-31 | 北京理工大学 | A kind of spherical nickeliferous carbonic acid manganese material and its preparation method and application |
| CN107910525A (en) * | 2017-11-16 | 2018-04-13 | 中山大学 | A kind of preparation method of N doping manganese carbonate and its compound |
| CN110504437A (en) * | 2019-08-30 | 2019-11-26 | 浙江大学山东工业技术研究院 | A kind of coated porous sodium manganate composite material and preparation method of polypyrrole and application |
| CN112661189A (en) * | 2020-12-25 | 2021-04-16 | 陕西科技大学 | Manganese carbonate nano material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105826522B (en) | 2018-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104201323B (en) | The preparation method of alumina-coated lithium cobaltate cathode material | |
| CN104538207B (en) | TiNb2O7The preparation method of/carbon nano tube compound material and using the material as the lithium-ion capacitor of negative pole | |
| CN104638219A (en) | Composite diaphragm for lithium-selenium battery and preparation method of composite diaphragm | |
| CN100435390C (en) | Synthesizing lithium ion cell positive material fluorophosphoric vanadium-lithium by sol-gel method | |
| CN104868104A (en) | Two-dimensional layered titanium carbide/metal ion composite material and application thereof | |
| CN105789615A (en) | Modified lithium nickel cobalt manganese cathode material and preparation method thereof | |
| CN106960955A (en) | Ternary cathode material of lithium ion battery of vanadium sulfide cladding and preparation method thereof | |
| CN104485442A (en) | Preparation method of self-assembled ball-flower type cathode material for lithium ion battery | |
| CN103956493B (en) | The preparation method of carbon cladding hierarchical organization LiFePO4 | |
| CN104993116B (en) | A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method | |
| CN105826522A (en) | Method for preparing in-situ carbon coated manganese carbonate for negative electrode of lithium ion battery | |
| CN111162256A (en) | Mixed polyanion type sodium ion battery positive electrode material and preparation thereof | |
| CN104466110B (en) | Preparation method of high-performance lithium ion battery negative electrode material | |
| CN104577072A (en) | Preparation method of graphene-oxide-based MoO2 high-performance electrode material of lithium/sodium ion battery | |
| CN102249297A (en) | Method for preparing lithium titanate powder | |
| CN110615480A (en) | Method for preparing layered lithium manganate material by dynamic hydrothermal method | |
| CN104292100B (en) | Terephthalic acid calcium is as the application of lithium ion battery negative material | |
| CN109873154A (en) | A kind of preparation method of the bimetallic oxide negative electrode material of lithium ion battery | |
| CN105481004B (en) | A kind of high electric property tin dioxide nanometer tube and preparation method thereof | |
| CN103413940B (en) | A kind of synthetic method of positive material nano lithium manganese phosphate of lithium ion battery | |
| CN108002356A (en) | δ-VOPO4Ultrathin nanometer piece and its controllable method for preparing and application | |
| CN103367705A (en) | Double-layer cladded composite lithium ion positive material and preparation method thereof | |
| CN107492648B (en) | Cotton-based carbon fiber/MnO/C material, preparation method and application | |
| CN106058195A (en) | Double-coated lithium vanadium phosphate anode material and preparation method thereof | |
| CN105514433A (en) | Preparation method of graphene lithium ion battery anode material doped with copper zinc tin sulfide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |