CN103840138A - Sn/C composite material prepared by utilization of algas and applications thereof - Google Patents
Sn/C composite material prepared by utilization of algas and applications thereof Download PDFInfo
- Publication number
- CN103840138A CN103840138A CN201410037831.6A CN201410037831A CN103840138A CN 103840138 A CN103840138 A CN 103840138A CN 201410037831 A CN201410037831 A CN 201410037831A CN 103840138 A CN103840138 A CN 103840138A
- Authority
- CN
- China
- Prior art keywords
- composite material
- carbonization
- algae
- algas
- 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
Images
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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a Sn/C composite material prepared by utilization of algas and applications thereof. A preparation method of the Sn/C composite material includes steps of: (1) dissolving SnCl4-H2O (1/5) into alcohol until the solution is clear to obtain a precursor solution having a concentration of 0.2-0.8 M; (2) cleaning the algas with a mixed solution of formaldehyde and deionized water, and removing impurities; (3) dipping the cleaned algas in the precursor solution at room temperature for 1-4 h, filtering and drying; and (4) mixing the dried algas with a DMF solution of polystyrene having a weight percent of 10-30%, raising the temperature to 400-1000 DEG C under the protection of nitrogen or argon at a temperature rising rate of 5-20 DEG C/min to perform carbonization for 2-7 h, cooling after carbonization, and grinding to obtain the Sn/C composite material. The Sn/C composite material comes from the algas adsorbing tin ions. The raw materials have wide sources and are easily available. The method is prone to industrial application. The preparation technology is simple and environmental-friendly. The Sn/C composite material when being used as an anode material of a lithium ion battery has good cycle performances and coulombic efficiency.
Description
(1) technical field
The present invention relates to a kind ofly utilize Sn/C composite material that algae makes and the application as lithium ion battery negative material thereof, and the lithium ion battery making thus.
(2) background technology
Lithium ion battery is the novel green high-energy secondary battery occurring early 1990s, has become the emphasis that competitively research and develop countries in the world.In the selection of positive and negative electrode material, positive electrode must be selected the lithium intercalation compound of high potential, and negative material must be selected the lithium intercalation compound of electronegative potential.Negative material is the chief component of lithium ion battery, and the quality of negative material performance directly has influence on the performance of lithium ion battery.Lithium cell cathode material has Carbon Materials, carbon compound and non-Carbon Materials, is Carbon Materials and apply maximum.At present, exploitation and the lithium ion battery negative material using mainly contain graphite, soft carbon, hard carbon etc., and wherein the theoretical specific capacity of graphite cathode material can reach 372mAh/g.But due to the restriction of the architectural characteristic of graphite own, the development of graphite cathode material has also run into bottleneck, specific capacity has reached the limit, can not meet the desired large current capacity etc. that continues of large-sized power battery.For meeting the instructions for use of electrokinetic cell high-energy-density and high-specific-power, the new system of the negative material using Sn as lithium ion battery received much concern in recent years.The advantage of Sn has: its theoretical specific capacity is 993mAh/g; Two Sn are as the negative pole of lithium ion battery, and its operating voltage is higher than graphite, and therefore it,, in discharging and recharging, has the feature such as low electrical impedance and fail safe height; Three metallic tins can not form irreversible loss in electrolyte.
There is fatal problem in the negative material of the Sn that at present prepared by scientific research personnel: the variation of volume in charge and discharge process of Sn battery is larger, causes tin particles efflorescence to reduce the ability of storage lithium, thereby can make the capacity of battery reduce rapidly.
The recombination energy of carbon and tin effectively suppresses tin particles efflorescence, and in recent years, the carbon source that research institute uses was in polymer and sugar etc., and only a few derives from green carbon source.
(3) summary of the invention
First object of the present invention is to provide a kind of Sn/C composite material that utilizes algae to make, and this Sn/C composite material derives from algae absorption tin metal ion, raw material sources extensively, be easy to get, be easy to industrializing implementation; Preparation technology is simple, environmentally friendly; The Sn/C composite material making has good cycle performance and coulomb efficiency in the time applying as lithium ion battery negative material.
Second object of the present invention is to provide the application of described Sn/C composite material as lithium ion battery negative material.
The 3rd object of the present invention is to provide the lithium ion battery using described Sn/C composite material as negative material.
Illustrate technical scheme of the present invention below.
The invention provides a kind of Sn/C composite material that utilizes algae, the preparation method of described Sn/C composite material comprises the steps:
(1) get SnCl
45H
2o is dissolved in alcohol, until clarification, the precursor solution of formation 0.2～0.8M;
(2) mixed solution cleaning, the removal of impurities of formaldehyde and deionized water for algae;
(3) under room temperature condition, clean algae is soaked 1～4 hour in precursor solution, filtered, dry;
(4) material of oven dry and the DMF(N of the polystyrene (PS) that mass fraction is 10～30% that step (3) are obtained; dinethylformamide) solution mixing; then under nitrogen or argon shield, rise to 400～1000 ℃ with the heating rate of 5～20 ℃/min and carry out carbonization; carbonization time 2～7 hours, cooling after carbonization, grinding obtains Sn/C composite material.
In described step (1), the concentration of precursor solution is preferably 0.3～0.6M, and more preferably 0.4～0.5M, most preferably is 0.4M.
In described step (2), selection for algae does not have special requirement, the Basic Mechanism of algae absorption tin metal ion is the surface complexation effect between metal cation and frustule function base, and in frustule, the contained hydroxyl of alginates, amino, carboxyl etc. play an important role in absorption, can suppress to a great extent the efflorescence of tin particles in charge and discharge process.The present invention specifically adopts spirulina, and it is a kind of many cells filamentous algae, is rich in protein (55%～70%).
In described step (3), the soak time of algae in precursor solution is preferably 1～2 hour.
In described step (4), the mass fraction of PS is preferably 20～25%, most preferably is 20%; Heating rate is preferably 5～18 ℃/min, and more preferably 5～10 ℃/min, most preferably is 5 ℃/min; Carburizing temperature is preferably 500～600 ℃, most preferably is 600 ℃; Carbonization time is preferably 2～4 hours, more preferably 4 hours.
The present invention is concrete recommends described Sn/C composite material to carry out in accordance with the following steps:
(1) get appropriate SnCl
45H
2o is dissolved in alcohol, until clarification, the precursor solution of formation 0.4～0.5M;
(2) algae is cleaned removal of impurities with the mixed solution of formaldehyde and deionized water (volume ratio 1:1);
(3) under room temperature condition, clean algae is soaked 1～2 hour in precursor solution, finally by filtration of material oven dry;
(4) material of step (4) being dried and the mass fraction PS(polystyrene that is 20～25%) DMF(N; dinethylformamide) solution mixing; then under nitrogen or argon shield, rise to 500～600 ℃ with the heating rate of 5～10 ℃/min and carry out carbonization; carbonization time 2～4 hours, cooling after carbonization, grinding obtains Sn/C composite material.
Sn/C composite material described in the present invention also provides is as the application of lithium ion battery negative material, and wherein the preparation of lithium ion battery adopts conventional method.
Finally, the present invention also provides the lithium ion battery using described Sn/C composite material as negative material.
Compared with prior art, its beneficial effect is mainly reflected in the present invention:
(1) in the present invention, algae, as biological template and part carbon source, utilizes its absorption Sn, can suppress to a great extent the efflorescence of tin particles in charge and discharge process.
(2) alga-derived extensively, be easy to get, be easy to industrializing implementation; Preparation technology is simple, without waste gas discharge of wastewater, thereby environmentally friendly.
(3) the present invention re-uses polystyrene to carry out carbon coated on the basis of algae absorption Sn element, and prepared Sn/C composite material shows good cycle performance and a coulomb efficiency while application as lithium ion battery negative material.
(4) accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the prepared Sn/C composite material of embodiment 1.
Fig. 2 is the figure of the cycle performance of the prepared simulation lithium ion battery of embodiment 1.
(5) specific implementation method
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited to this.
Embodiment 1
Get appropriate SnCl
45H
2o is dissolved in alcohol, until clarification, the precursor solution of formation 0.4M.Meanwhile, with the mixed solution of formaldehyde and deionized water (volume ratio 1:1), blunt top spirulina (deriving from marine organisms center, by Zhejiang Polytechnical University's screening and culturing in pure water) is washed to several times, removal of impurities.In room temperature, then clean blunt top spirulina is soaked 1 hour in presoma, finally by filtration of material oven dry.It is coated that the PS/DMF that is 20% with mass fraction by the material of oven dry carries out carbon, and then under nitrogen or argon shield, rise to 600 ℃ with the heating rate of 5 ℃/min and carry out carbonization, carbonization time 4 hours, cooling after carbonization, grinding obtains Sn/C composite material.Fig. 1 is the XRD diffraction pattern of this material, and reference standard card is the tin of tetragonal structure.
Make as follows electrode with the prepared Sn/C composite material of embodiment 1.
Mass ratio with 70:15:15 takes respectively Sn/C composite material: super-P: poly-inclined to one side tetrafluoroethene, after grinding evenly, make electrode, and metal lithium sheet is anodal, electrolyte is 1mol/L LiPF
6/ EC – DMC (1:1), polypropylene microporous film is barrier film, is assembled into simulation lithium ion battery.Fig. 2 is the cycle performance curve of respective battery in 0.05C, 0.005～2.7V voltage range, show that surveyed battery has good cycle performance and approaches 99% coulomb efficiency at 0.05C, can find out that the Sn/C composite material that made by embodiment 1 discharge capacity after 0.05C circulation 80 times approaches 400mAh/g(Fig. 2), cycle performance excellence.
Embodiment 2
Get appropriate SnCl
45H
2o is dissolved in alcoholic solution, until clarification, the precursor solution of formation 0.4M.Meanwhile, blunt top spirulina is washed to several times, removal of impurities with the mixed solution of formaldehyde and deionized water (volume ratio 1:1).In room temperature, then clean blunt top spirulina is soaked 2 hours in presoma, finally by filtration of material oven dry.The PS(polystyrene that is 25% with mass fraction by the material of oven dry)/DMF(dimethyl formamide) to carry out carbon coated; then under nitrogen or argon shield, rise to 600 ℃ with the heating rate of 10 ℃/min and carry out carbonization; carbonization time 2 hours, cooling after carbonization, grinding obtains Sn/C composite material.
Make electrode with prepared Sn/C composite material by the method for embodiment 1, be assembled into simulation lithium ion battery, the discharge capacity after 0.05C circulation 80 times approaches 370mAh/g, and cycle performance, reversibility are good.
Embodiment 3
Get appropriate SnCl
45H
2o is dissolved in alcoholic solution, until clarification, the precursor solution of formation 0.5M.Meanwhile, blunt top spirulina is washed to several times, removal of impurities with the mixed solution of formaldehyde and deionized water (volume ratio 1:1).In room temperature, then clean blunt top spirulina is soaked 1 hour in presoma, finally by filtration of material oven dry.The PS(polystyrene that is 20% with mass fraction by the material of oven dry)/DMF(dimethyl formamide) to carry out carbon coated; then under nitrogen or argon shield, rise to 500 ℃ with the heating rate of 5 ℃/min and carry out carbonization; carbonization time 4 hours, cooling after carbonization, grinding obtains Sn/C composite material.
Make electrode with prepared Sn/C composite material by the method for embodiment 1, be assembled into simulation lithium ion battery, the discharge capacity after 0.05C circulation 80 times approaches 350mAh/g, and cycle performance, reversibility are good.
Embodiment 4
Get appropriate SnCl
45H
2o is dissolved in alcoholic solution, until clarification, the precursor solution of formation 0.5M.Meanwhile, blunt top spirulina is washed to several times, removal of impurities with the mixed solution of formaldehyde and deionized water (volume ratio 1:1).In room temperature, then clean blunt top spirulina is soaked 1 hour in presoma, finally by filtration of material oven dry.The PS(polystyrene that is 20% with mass fraction by the material of oven dry)/DMF(dimethyl formamide) to carry out carbon coated; then under nitrogen or argon shield, rise to 500 ℃ with the heating rate of 10 ℃/min and carry out carbonization; carbonization time 2 hours, cooling after carbonization, grinding obtains Sn/C composite material.
Make electrode with prepared Sn/C composite material by the method for embodiment 1, be assembled into simulation lithium ion battery, the discharge capacity that 0.05C circulates after 80 times approaches 320mAh/g.
Claims (10)
1. a Sn/C composite material that utilizes algae to make, the preparation method of described Sn/C composite material comprises the steps:
(1) get SnCl
45H
2o is dissolved in alcohol, until clarification, the precursor solution of formation 0.2～0.8M;
(2) mixed solution cleaning, the removal of impurities of formaldehyde and deionized water for algae;
(3) under room temperature condition, clean algae is soaked 1～4 hour in precursor solution, filtered, dry;
(4) the DMF solution of the polystyrene that the material of oven dry step (3) being obtained is 10～30% with mass fraction mixes; then under nitrogen or argon shield, rise to 400～1000 ℃ with the heating rate of 5～20 ℃/min and carry out carbonization 2～7 hours, cooling after carbonization, grinding obtains Sn/C composite material.
2. Sn/C composite material as claimed in claim 1, is characterized in that: described algae is selected from spirulina.
3. Sn/C composite material as claimed in claim 1 or 2, is characterized in that: in step (4), heating rate is 5～18 ℃/min.
4. Sn/C composite material as claimed in claim 1 or 2, is characterized in that: in step (4), heating rate is 5～10 ℃/min.
5. Sn/C composite material as claimed in claim 1 or 2, is characterized in that: in step (4), carburizing temperature is 500～600 ℃, and carbonization time is 2～4 hours.
6. Sn/C composite material as claimed in claim 1 or 2, is characterized in that: in step (4), carburizing temperature is 600 ℃, and carbonization time is 4 hours.
7. Sn/C composite material as claimed in claim 1 or 2, is characterized in that described Sn/C composite material carries out in accordance with the following steps:
(1) get appropriate SnCl
45H
2o is dissolved in alcohol, until clarification, the precursor solution of formation 0.4～0.5M;
(2) algae is cleaned removal of impurities with the mixed solution of formaldehyde and deionized water;
(3) under room temperature condition, clean algae is soaked 1～2 hour in precursor solution, finally by filtration of material oven dry;
(4) the DMF solution of the polystyrene that the material of step (4) being dried is 20～25% with mass fraction mixes; then under nitrogen or argon shield, rise to 500～600 ℃ with the heating rate of 5～10 ℃/min and carry out carbonization; carbonization time 2～4 hours, cooling after carbonization, grinding obtains Sn/C composite material.
8. Sn/C composite material as claimed in claim 7, is characterized in that: in described step (4), heating rate is 5 ℃/min, and carburizing temperature is 600 ℃, and carbonization time is 4 hours.
9. Sn/C composite material as claimed in claim 1 is as the application of lithium ion battery negative material.
10. the lithium ion battery making as negative material using Sn/C composite material claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410037831.6A CN103840138B (en) | 2014-01-26 | 2014-01-26 | A kind of utilize algae obtained Sn/C composite material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410037831.6A CN103840138B (en) | 2014-01-26 | 2014-01-26 | A kind of utilize algae obtained Sn/C composite material and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103840138A true CN103840138A (en) | 2014-06-04 |
| CN103840138B CN103840138B (en) | 2016-03-02 |
Family
ID=50803422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410037831.6A Active CN103840138B (en) | 2014-01-26 | 2014-01-26 | A kind of utilize algae obtained Sn/C composite material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103840138B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109742360A (en) * | 2019-01-08 | 2019-05-10 | 福建师范大学 | There is one kind high capacity selenizing molybdenum-chlorella derived carbon to lack the preparation of layer compound cell negative electrode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102263236A (en) * | 2011-06-17 | 2011-11-30 | 山东轻工业学院 | Preparation method of meso-porous spherical lithium iron phosphate/carbon in-situ composite material |
| CN102509792A (en) * | 2011-10-22 | 2012-06-20 | 山东轻工业学院 | Biomimetic synthesis method of lithium vanadium phosphate/carbon nanometer composite mesoporous microspheres as positive electrode material of lithium ion battery |
| JP2012164616A (en) * | 2011-02-09 | 2012-08-30 | Nec Corp | Negative electrode material for secondary battery, and method for manufacturing the same |
| CN103050679A (en) * | 2012-12-26 | 2013-04-17 | 浙江工业大学 | Spherical hollow porous MnO/C composite material and application thereof |
-
2014
- 2014-01-26 CN CN201410037831.6A patent/CN103840138B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012164616A (en) * | 2011-02-09 | 2012-08-30 | Nec Corp | Negative electrode material for secondary battery, and method for manufacturing the same |
| CN102263236A (en) * | 2011-06-17 | 2011-11-30 | 山东轻工业学院 | Preparation method of meso-porous spherical lithium iron phosphate/carbon in-situ composite material |
| CN102509792A (en) * | 2011-10-22 | 2012-06-20 | 山东轻工业学院 | Biomimetic synthesis method of lithium vanadium phosphate/carbon nanometer composite mesoporous microspheres as positive electrode material of lithium ion battery |
| CN103050679A (en) * | 2012-12-26 | 2013-04-17 | 浙江工业大学 | Spherical hollow porous MnO/C composite material and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109742360A (en) * | 2019-01-08 | 2019-05-10 | 福建师范大学 | There is one kind high capacity selenizing molybdenum-chlorella derived carbon to lack the preparation of layer compound cell negative electrode material |
| CN109742360B (en) * | 2019-01-08 | 2022-03-29 | 福建师范大学 | Preparation method of high-capacity molybdenum selenide-chlorella derived carbon-less-layer composite battery anode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103840138B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102569759B (en) | Process for preparing materials of silicon-porous carbon negative electrodes of lithium-ion batteries | |
| CN104201323A (en) | Preparation method of alumina coated lithium cobaltate positive electrode material | |
| CN104157852A (en) | Sulfur positive electrode of lithium sulfur battery and preparation method | |
| CN103094573A (en) | Preparation method of silicon-based/graphene composite | |
| CN102368545A (en) | Preparation technology of lithium manganate electrode material doping and surface fluoride cladding | |
| CN104157849A (en) | Method for preparing elemental sulfur and mesoporous carbon composite material | |
| CN103050679A (en) | Spherical hollow porous MnO/C composite material and application thereof | |
| CN109585832B (en) | Sulfur-doped microcrystalline graphite, preparation method thereof and application of sulfur-doped microcrystalline graphite as negative electrode material of sodium-ion battery | |
| CN105810929A (en) | Treatment method for reducing residual alkalis on surface of high nickel material | |
| CN113948681B (en) | Biomass-based hard carbon compound composite material and preparation method and application thereof | |
| CN104401974A (en) | Preparation method of high capacity carbon cathode material for lithium ion batteries | |
| CN104966814A (en) | High-security metallic lithium cathode and preparation method thereof | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN105502389A (en) | Method for preparing activated carbon material for supercapacitor electrode from calyx seu fructus physalis persistent calyxes | |
| CN104157859B (en) | A kind of method preparing high performance lithium ionic cell cathode material for raw material with bagasse | |
| CN105098183A (en) | Preparation for carbon anode material of lithium ion battery by using rice hull as raw material | |
| CN111646510A (en) | High-rate titanium niobium oxide microsphere and preparation method and application thereof | |
| CN114318368A (en) | Special electrolytic manganese dioxide for lithium manganate battery and preparation method and application thereof | |
| CN103441280A (en) | Method for preparing negative pole material of lithium ion battery through hydrothermally activated sisal carbon fibers | |
| CN104600260A (en) | C/Ni/S composite material prepared from absorbent cotton and preparation method and application thereof | |
| CN103840138B (en) | A kind of utilize algae obtained Sn/C composite material and application | |
| CN111883368A (en) | Pine nut shell derived carbon material/triazine polymer derived carbon material, preparation method and application thereof, and double-carbon sodium ion hybrid capacitor | |
| CN115832294A (en) | Method for preparing biomass-based hard carbon composite negative electrode through magnetron sputtering | |
| CN102723477A (en) | Preparation method of laminated lithium-enriched cathode material | |
| CN113363574B (en) | Polymer electrolyte and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |