CN108899506A - A kind of porous nano carbon coating manganate cathode material for lithium and preparation method thereof - Google Patents
A kind of porous nano carbon coating manganate cathode material for lithium and preparation method thereof Download PDFInfo
- Publication number
- CN108899506A CN108899506A CN201810711205.9A CN201810711205A CN108899506A CN 108899506 A CN108899506 A CN 108899506A CN 201810711205 A CN201810711205 A CN 201810711205A CN 108899506 A CN108899506 A CN 108899506A
- Authority
- CN
- China
- Prior art keywords
- carbon coating
- porous nano
- lithium
- nano carbon
- cathode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/028—Positive 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
Abstract
The invention belongs to technical field of lithium ion battery electrode, and in particular to a kind of porous nano carbon coating manganate cathode material for lithium and preparation method thereof.The present invention by by LiMn2O4 be added to containing phenol, aldehyde, basic catalyst mixing salt solution in, react to obtain wet gel by gel polymerisation, then by exchange of solvent, high-temperature roasting obtain porous nano carbon coating manganate cathode material for lithium.Compared with common nano-sized carbon, porous nano carbon has good electric conductivity and stable structure, good clad can be formed on LiMn2O4 surface, reduce its directly contacting between electrolyte, reduce corrosion function of the electrolyte to lithium manganate material, the electric conductivity that material can also be improved to a certain extent simultaneously, reduces the reunion of lithium manganate material, to improve the chemical stability and cycle performance of lithium manganate material.
Description
Technical field
The invention belongs to technical field of lithium ion battery electrode, and in particular to a kind of porous nano carbon coating LiMn2O4
Positive electrode and preparation method thereof.
Background technique
Lithium manganate having spinel structure LiMn2O4Being that Hunter is obtained first in 1981 has three-dimensional lithium ion tunnel just
Pole material, compared to traditional positive electrode such as cobalt acid lithium, LiMn2O4 have resourceful, at low cost, pollution-free, safety is good, times
The advantages that rate performance is good is ideal power battery anode material.
LiMn2O4 is in early 1990s Sony Corporation of Japan as the concentration research and development of anode material for lithium-ion batteries
After the lithium ion battery for releasing commercialization, but it is more unstable at high temperature, and easily to spinel structure in charge and discharge process
Transformation, causes capacity attenuation too fast, the disadvantage of high temperature circulation difference limits always the material to be made in practical lithium-ion
With.
In recent years, various nano-carbon materials are due to its unique structure, good chemical stability and mechanical stability, compared with
Big surface area and preferable electric conductivity are also gradually applied to sharp electronic cell field by extensive concern.However at present
Electrode material carbon coating process is unable to control coating thickness, and carbon coating layer is blocked up to will increase lithium ion transport path, leads to electricity
Pole material impedance is excessive.
Summary of the invention
The primary purpose of the present invention is that providing a kind of preparation method of porous nano carbon coating manganate cathode material for lithium.It should
Method realizes the clad controllable preparation of porous nano carbon material by control sol-gel process；And method is easy to operate, former
Expect cheap, can improve the chemical stability of lithium manganate material, solves capacity rapid decay etc. during high voltage cycle and ask
Topic.
Another object of the present invention is to provide one kind porous nano carbon coating LiMn2O4 as made from above-mentioned preparation method
Positive electrode.The porous nano carbon coating manganate cathode material for lithium has excellent chemical stability and cyclical stability.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of porous nano carbon coating manganate cathode material for lithium, includes the following steps：
(1) weighing phenol, aldehyde monomer are added in reaction vessel 1, and water are added, and base catalyst is added, stirs evenly；Then
LiMn is added2O4, stirring forms the uniform suspension of black under water-bath, then is injected into reaction vessel 2, and reaction is held
Device 2 seals, and carries out gel polymerisation reaction；
(2) after reaction time cut-off, the wet gel taken out from reaction vessel 2 is put into organic solvent and carries out
Then exchange of solvent is dried at room temperature；
(3) by the gel after drying in N2Or roasted under inert gas shielding, then natural cooling, grinds, and sieving obtains
The porous nano carbon coating manganate cathode material for lithium.
LiMn is added in the present invention2O4Coating thickness can control by control mixing time afterwards, realize porous nano carbon materials
Expect the controllable preparation of clad, whipping process is the pre- collecting process of resorcinol and formaldehyde, this time is longer, theoretically coats
Carbon coating layer on LiMn2O4 surface is thicker.Porous nano carbon coating manganate cathode material for lithium produced by the present invention has excellent
Chemical stability and cyclical stability.
Preferably, phenol monomer described in step (1) is at least one of resorcinol, hydroquinone.
Preferably, aldehyde monomer described in step (1) is at least one of formaldehyde, acetaldehyde, furfural.
Preferably, base catalyst described in step (1) is at least one of natrium carbonicum calcinatum, potassium carbonate.
Preferably, according to the mass fraction, phenol monomer described in step (1) is 5-10 mass parts, and aldehyde monomer is 8-60 mass
Part, water is 40-70 mass parts, LiMn2O4For 10-40 mass parts, wherein the molar ratio of phenol monomer and aldehyde monomer is 1:(2-7), alkali
Catalyst amount is the 1/1000-5/1000 of phenol monomer and aldehyde monomer gross mass.
It is furthermore preferred that phenol monomer described in step (1) is 8-10 mass parts, aldehyde monomer is 10-20 mass parts, water 40-
50 mass parts, LiMn2O4For 20-30 mass parts, wherein the molar ratio of phenol monomer and aldehyde monomer is 1:(2-7)；Base catalyst dosage
It is the 1/1000 of phenol monomer and aldehyde monomer gross mass.
Preferably, the temperature of water-bath described in step (1) is 20-60 DEG C, more preferably 40-60 DEG C.
Preferably, LiMn is added in step (1)2O4The time stirred under water-bath afterwards is 10-30 minutes, more preferable 20-30
Minute；Mixing speed is preferably 100-300rpm.
Preferably, gel polymerisation reaction temperature described in step (1) is 60-80 DEG C, and the reaction time is 3-8 days；More preferably
, gel polymerisation reaction temperature is 70-80 DEG C, and the reaction time is 7-8 days.
Preferably, the reaction vessel 1 is this field conventional vessel, no particular/special requirement；The reaction vessel 2 is ampoule
Bottle or other sealable glass containers.
Preferably, organic solvent described in step (2) is at least one of acetone, ether, chloroform.
Preferably, the exchange of solvent time described in step (2) is 2-4 days, changes an organic solvent daily；More preferably 3-
4 days.
Preferably, drying time described in step (2) is 12-48 hours；More preferably 24-48 hours.
Preferably, the temperature of roasting described in step (3) is 500-800 DEG C, and the time is 2-5 hours；It is furthermore preferred that described
The temperature of roasting is 700-800 DEG C, and the time is 3-4 hours.
Preferably, hydrogel warms are roasted to 500-800 DEG C with the rate of 2-10 DEG C/min in step (3).
Preferably, sieving described in step (3) refers to 500-800 mesh, more preferably 700-800 mesh.
Compared with prior art, the present invention has the following advantages and beneficial effects：
Compared with common nano-sized carbon, porous nano carbon has good electric conductivity and stable structure, can be in LiMn2O4
Surface forms good clad, reduces its directly contacting between electrolyte, reduces electrolyte and invade lithium manganate material
Erosion effect, while the electric conductivity of material can also be improved to a certain extent, the reunion of lithium manganate material is reduced, to improve mangaic acid
The chemical stability and cycle performance of lithium material.The present invention by by LiMn2O4 be added to containing phenol, aldehyde, basic catalyst it is mixed
It closes in salting liquid, reacts to obtain wet gel by gel polymerisation, porous nano carbon is then obtained by exchange of solvent, high-temperature roasting
Coat manganate cathode material for lithium, method is simple, cost of material it is low, it can be achieved that porous nano carbon material clad controllable preparation.
Also, porous nano carbon coating manganate cathode material for lithium produced by the present invention has excellent chemical stability and stable circulation
Property.
Detailed description of the invention
Fig. 1 is the N of the different LiMn2O4s of embodiment 12Adsorption-desorption isothermal, porous nano carbon coating LiMn2O4 therein
Refer to the carbon-coated LiMn of porous nano prepared by embodiment 12O4Material powder.
Fig. 2 is the pore size distribution curve of the different LiMn2O4s of embodiment 1, and porous nano carbon coating LiMn2O4 therein refers to reality
Apply the carbon-coated LiMn of porous nano of the preparation of example 12O4Material powder.
Fig. 3 is the XRD curve of the different LiMn2O4s of embodiment 1, and porous nano carbon coating LiMn2O4 therein refers to embodiment 1
The carbon-coated LiMn of the porous nano of preparation2O4Material powder.
Fig. 4 is the cyclic voltammetry curve of the different LiMn2O4s of embodiment 1, and porous nano carbon coating LiMn2O4 therein refers to reality
Apply the carbon-coated LiMn of porous nano of the preparation of example 12O4Material powder.
The 2nd time of LiMn2O4 when Fig. 5 is 25 DEG C in embodiment 1, the 50th time, the 100th charging and discharging curve.
Carbon coating LiMn when Fig. 6 is 25 DEG C in embodiment 12O4The 2nd time, the 50th time, the 100th charging and discharging curve.
Fig. 7 is the cycle performance of the different LiMn2O4 samples of embodiment 1, and porous nano carbon coating LiMn2O4 therein refers to reality
Apply the carbon-coated LiMn of porous nano of the preparation of example 12O4Material powder.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1：
(1) 9.706g resorcinol, 14.309g formaldehyde (molar ratio 1 are weighed:2) it is added in beaker, and moisturizing 45g, then
The LiMn of 0.024g natrium carbonicum calcinatum (base catalyst) and 25g is added2O4.20 minutes formation black is stirred under 50 DEG C of water-bath
Uniform suspension, then be injected into ampoule bottle, ampoule bottle is sealed using high temperature, 70 DEG C of constant temperature is then placed within and dries
Gel polymerisation is reacted 3 days in case.
(2) after reaction time cut-off, the resorcinol formaldehyde wet gel that (1) obtains is taken out from ampoule bottle, is put into third
The exchange of solvent that 3 days by a definite date are carried out in ketone changes an acetone daily, then dries 24 hours at room temperature for 25 DEG C.
(3) resorcinol formaldehyde (RF) gel after drying N has been placed in2In the tube furnace of protection, with the speed of 5 DEG C/min
RF hydrogel warms to 800 DEG C, are roasted 2 hours, then allow its natural cooling, 800 meshes are ground and crossed using agate mortar by rate,
Obtain the carbon-coated LiMn of porous nano2O4Material powder (hereinafter referred to as carbon coating LiMn2O4)。
Using Full-automatic physical adsorption instrument to carbon coating LiMn obtained2O4Material pore structure is tested, and adsorbing medium is
N2, sample pretreatment temperature is 250 DEG C, and test temperature is -196 DEG C, then passes through low temperature N2Physisorphtion is measured.Kong Jie
Structure test result is shown in Fig. 1, Fig. 2, table 1, shows carbon coating LiMn2O4There is pore structure very rich.
By X-ray powder diffraction and pore structure test to carbon coating LiMn2O4Structure carry out phenetic analysis, measure item
Part：Using Cu-K α radiation source, minimum measuring angle is 0.02 °, 2 θ=5 °~90 ° of scanning range.As a result see Fig. 3, it is pure
LiMn2O4With carbon coating LiMn2O4All there is diffraction in 18.7 °, 35.4 °, 41.2 °, 58.5 °, 70.4 °, 74.3 °, 88.3 °
Peak, it is consistent with the standard diffraction peak of spinal LiMn_2O_4 (PDF#35-782) card, belong to very typical spinel structure
Characteristic peak.After X-ray powder diffraction shows the coated porous conductive nano carbon-coating in surface, there is no change LiMn2O4Crystal knot
Structure.
By evengranular carbon coating LiMn2O4Material powder uses 1.2t/cm2Pressure suppress 30s, be made with a thickness of
The sample of 2mm measures carbon coating LiMn with four probe resistance rate testers2O4The resistivity of positive electrode.With the pressure of 10N
4 probes are vertically pressed on sample surfaces, and two probe galvanization I on the outside simultaneously, then have voltage U in inside
It is generated between two probes, electricalresistivityρ is calculated by formula (1)：
ρ=(U/I) × F (D/S) × F (W/S) × W × Fsp (1)
In formula (1)：D, W is respectively the diameter of sample, thickness, and S is average probe spacing, and F (D/S), F (W/S) are respectively
The diameter of sample, thickness modifying factor, FspFor probe spacing correction factor.Four probe resistance rate test results are shown in Table 2, show carbon
The LiMn of cladding2O4Electric conductivity behave oneself best.
With carbon coating LiMn obtained by the embodiment of the present invention 12O4For positive electrode, acetylene black gathers inclined fluorine as conductive agent
Ethylene (PVDF) is used as binder, mass ratio 85:10:5.It is molten that PVDF is first dissolved in suitable N methyl pyrrolidone (NMP)
Agent, and acetylene black is added and stirs evenly, add LiMn2O4, stirring 5 hours or more, obtain uniform pasty slurry.Then will
Obtained slurry is applied in aluminum foil current collector, and is painted with the drying of vacuum oven high temperature 24 hours that horse back is placed in 110 DEG C,
The circular electric pole piece that radius is 4.5mm is gone out by sheet-punching machine after cooling, as positive plate.Cathode uses metal lithium sheet (radius
For 4.5mm, with a thickness of 0.1mm), electrolyte selects EC (ethylene carbonate)+EMC (methyl ethyl carbonate) of 1.0mol/L LiPF6
+ DMC (dimethyl carbonate) (volume ratio 1:1:1) solution, then with the microporous polypropylene membrane (diaphragm diameter of 2400 type of Celgard
Diaphragm for 14mm) as battery is assembled into 2032 type button cells.
Cyclic voltammetric survey is carried out with the scanning voltage range button type battery of the sweep speed of 10mV/s and 3.0~4.5V
Examination.As a result see Fig. 4.It can see by cyclic voltammetry curve figure, after carrying out porous nano carbon coating to LiMn2O4,3.8V is extremely
Redox peaks between 4.5V reduce.This is mainly that carbon coating layer is able to suppress positive active material in charge and discharge cycles process
The dissolution of middle Mn, carbon coating layer are also used as protective layer and effectively inhibit to send out between LiMn2O4 active material surface and electrolyte
Raw side reaction reduces electrolyte decomposition in the SEI film that positive electrode surface is formed, reduces Li+Impedance in mass transport process improves
The efficiency of positive discharge.
Charge-discharge test is carried out with 1C multiplying power at 25 DEG C.LiMn2O4, carbon coating LiMn2O4Second of specific discharge capacity difference
For 103mAh/g, 96mAh/g, carbon coating LiMn2O4Capacity retention ratio is 92.24% after 100 circulations, and pure LiMn2O4?
Capacity retention ratio is only 84.72% after 100 circulations.
The pore structure data of the different LiMn2O4s of table 1
The average resistivity of the different LiMn2O4s of table 2
Embodiment 2：
(1) weigh 9.706g hydroquinone, 14.309g acetaldehyde to be added in beaker, and moisturizing 40g, add 0.03g without
The LiMn of aqueous carbonate potassium (base catalyst) and 30g2O4.It is stirred under 50 DEG C of water-bath and forms within 15 minutes the uniform suspension of black,
It is injected into ampoule bottle again, ampoule bottle is sealed using high temperature, is then placed within gel polymerisation in 70 DEG C of constant temperature oven
Reaction 7 days.
(2) after reaction time cut-off, the hydroquinone acetaldehyde wet gel that (1) obtains is taken out from ampoule bottle, is put into chlorine
The exchange of solvent that 3 days by a definite date are carried out in imitative, changes a chloroform daily, then dries 24 hours at room temperature for 25 DEG C.
(3) gel after drying N has been placed in2In the tube furnace of protection, with the rate of 10 DEG C/min by hydrogel warms extremely
It 600 DEG C, roasts 2.5 hours, then allows its natural cooling, 800 meshes are ground and crossed using agate mortar, obtain porous nano carbon
The LiMn of cladding2O4Material powder (hereinafter referred to as carbon coating LiMn2O4)。
Using Full-automatic physical adsorption instrument to carbon coating LiMn obtained2O4Material pore structure is tested, and test result is shown in
Table 3 shows carbon coating LiMn2O4There is pore structure very rich.
Carbon coating LiMn is measured using four probe resistance rate testers2O4The resistivity of positive electrode.Test result is shown in Table
4, show carbon-coated LiMn2O4Electric conductivity behave oneself best.
By 1 method of the embodiment of the present invention, using carbon coating LiMn manufactured in the present embodiment2O4For positive active material assembling
At 2032 type button cells and test its performance.Second of specific discharge capacity is respectively 93mAh/g, and capacity is protected after 100 circulations
Holdup is 90.12%.
The pore structure data of the different LiMn2O4s of table 3
The average resistivity of the different LiMn2O4s of table 4
Embodiment 3：
(1) weighing 9.706g resorcinol, 52.3g furfural are added in beaker, and moisturizing 60g, and it is anhydrous to add 0.06g
The LiMn of potassium carbonate (base catalyst) and 25g2O4.It is stirred under 50 DEG C of water-bath and forms within 10 minutes the uniform suspension of black, then
It is injected into ampoule bottle, ampoule bottle is sealed using high temperature, it is anti-to be then placed within gel polymerisation in 60 DEG C of constant temperature oven
It answers 5 days.
(2) after reaction time cut-off, the hydroquinone acetaldehyde wet gel that (1) obtains is taken out from ampoule bottle, is put into second
The exchange of solvent that 2 days by a definite date are carried out in ether changes an ether daily, then dries 24 hours at room temperature for 25 DEG C.
(3) gel after drying N has been placed in2In the tube furnace of protection, with the rate of 8 DEG C/min by hydrogel warms extremely
It 800 DEG C, roasts 4 hours, then allows its natural cooling, 800 meshes are ground and crossed using agate mortar, obtain porous nano carbon packet
The LiMn covered2O4Material powder (hereinafter referred to as carbon coating LiMn2O4)。
Using Full-automatic physical adsorption instrument to carbon coating LiMn obtained2O4Material pore structure is tested, and test result is shown in
Table 5 shows carbon coating LiMn2O4There is pore structure very rich.
Carbon coating LiMn is measured using four probe resistance rate testers2O4The resistivity of positive electrode.Test result is shown in Table
6, show carbon-coated LiMn2O4Electric conductivity behave oneself best.
By 1 method of the embodiment of the present invention, using carbon coating LiMn manufactured in the present embodiment2O4For positive active material assembling
At 2032 type button cells and test its performance.Second of specific discharge capacity is respectively 90mAh/g, and capacity is protected after 100 circulations
Holdup is 87.52%.
The pore structure data of the different LiMn2O4s of table 5
The average resistivity of the different LiMn2O4s of table 6
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium, which is characterized in that include the following steps：
(1) weighing phenol monomer, aldehyde monomer are added in reaction vessel 1, and water are added, and base catalyst is added, stirs evenly；Then
LiMn is added2O4, stirring forms the uniform suspension of black under water-bath, then is injected into reaction vessel 2, and reaction is held
Device 2 seals, and carries out gel polymerisation reaction；
(2) after reaction time cut-off, the wet gel taken out from reaction vessel 2 is put into organic solvent and carries out solvent
Exchange, is then dried at room temperature；
(3) by the gel after drying in N2Or roasted under inert gas shielding, then natural cooling, grinds, sieving, obtains described
Porous nano carbon coating manganate cathode material for lithium.
2. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium according to claim 1, feature exist
In phenol monomer described in step (1) is at least one of resorcinol, hydroquinone；
Aldehyde monomer described in step (1) is at least one of formaldehyde, acetaldehyde, furfural；
Base catalyst described in step (1) is at least one of natrium carbonicum calcinatum, potassium carbonate.
3. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium according to claim 1, feature exist
According to the mass fraction, phenol monomer described in step (1) is 5-10 mass parts, and aldehyde monomer is 8-60 mass parts, water 40-70
Mass parts, LiMn2O4For 10-40 mass parts, wherein the molar ratio of phenol monomer and aldehyde monomer is 1:(2-7)；Base catalyst dosage is
The 1/1000-5/1000 of phenol monomer and aldehyde monomer gross mass.
4. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium according to claim 1, feature exist
According to the mass fraction, phenol monomer described in step (1) is 8-10 mass parts, and aldehyde monomer is 10-20 mass parts, water 40-50
Mass parts, LiMn2O4For 20-30 mass parts, wherein the molar ratio of phenol monomer and aldehyde monomer is 1:(2-7)；Base catalyst dosage is
The 1/1000 of phenol monomer and aldehyde monomer gross mass.
5. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium according to claim 1, feature exist
In bath temperature described in step (1) is 20-60 DEG C；
LiMn is added in step (1)2O4The time stirred under water-bath afterwards is 10-30 minutes, mixing speed 100-300rpm.
6. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium according to claim 1, feature exist
In gel polymerisation reaction temperature described in step (1) is 60-80 DEG C, and the reaction time is 3-8 days.
7. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium according to claim 1, feature exist
In organic solvent described in step (2) is at least one of acetone, ether, chloroform；
The exchange of solvent time described in step (2) is 2-4 days, changes an organic solvent daily；
Drying time described in step (2) is 12-48 hours.
8. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium according to claim 1, feature exist
In the temperature of roasting described in step (3) is 500-800 DEG C, and the time is 2-5 hours.
9. a kind of preparation method of porous nano carbon coating manganate cathode material for lithium according to claim 1, feature exist
In, in step (3) with the rate of 2-10 DEG C/min by hydrogel warms to 500-800 DEG C roast；
Sieving described in step (3) refers to 500-800 mesh.
10. a kind of porous nano carbon coating manganate cathode material for lithium, which is characterized in that it is as described in any one of claim 1 to 9
A kind of porous nano carbon coating manganate cathode material for lithium preparation method be made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810711205.9A CN108899506A (en) | 2018-07-03 | 2018-07-03 | A kind of porous nano carbon coating manganate cathode material for lithium and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810711205.9A CN108899506A (en) | 2018-07-03 | 2018-07-03 | A kind of porous nano carbon coating manganate cathode material for lithium and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108899506A true CN108899506A (en) | 2018-11-27 |
Family
ID=64347616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810711205.9A Pending CN108899506A (en) | 2018-07-03 | 2018-07-03 | A kind of porous nano carbon coating manganate cathode material for lithium and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108899506A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116600888A (en) * | 2023-03-27 | 2023-08-15 | 广东邦普循环科技有限公司 | Carbon-coated lithium ion sieve for extracting lithium by electrochemical deintercalation method, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437318A (en) * | 2011-11-30 | 2012-05-02 | 奇瑞汽车股份有限公司 | Preparation method for silicon-carbon composite material, prepared silicon-carbon composite material, lithium ion battery anode containing silicon-carbon composite material and battery |
| CN102916178A (en) * | 2012-11-07 | 2013-02-06 | 彩虹集团公司 | Preparation method of carbon cladding modified lithium manganate anode material |
| CN105826531A (en) * | 2016-03-25 | 2016-08-03 | 河南鹏辉能源科技有限公司 | Preparation method for in-situ carbon-coated lithium nickel manganese oxide anode material and product thereof |
| CN106207169A (en) * | 2016-08-05 | 2016-12-07 | 宁波江东仑斯福环保科技有限公司 | A kind of preparation method of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode |
-
2018
- 2018-07-03 CN CN201810711205.9A patent/CN108899506A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437318A (en) * | 2011-11-30 | 2012-05-02 | 奇瑞汽车股份有限公司 | Preparation method for silicon-carbon composite material, prepared silicon-carbon composite material, lithium ion battery anode containing silicon-carbon composite material and battery |
| CN102916178A (en) * | 2012-11-07 | 2013-02-06 | 彩虹集团公司 | Preparation method of carbon cladding modified lithium manganate anode material |
| CN105826531A (en) * | 2016-03-25 | 2016-08-03 | 河南鹏辉能源科技有限公司 | Preparation method for in-situ carbon-coated lithium nickel manganese oxide anode material and product thereof |
| CN106207169A (en) * | 2016-08-05 | 2016-12-07 | 宁波江东仑斯福环保科技有限公司 | A kind of preparation method of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode |
Non-Patent Citations (1)
| Title |
|---|
| 张建峰: "LiMn2O4电极材料的碳包覆改性及电化学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116600888A (en) * | 2023-03-27 | 2023-08-15 | 广东邦普循环科技有限公司 | Carbon-coated lithium ion sieve for extracting lithium by electrochemical deintercalation method, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105449186B (en) | A kind of secondary cell and preparation method thereof | |
| CN103928672B (en) | A kind of positive electrode active material for lithium ion battery and preparation method thereof | |
| CN106207255B (en) | Organic electrolyte system lithium iodine secondary cell and preparation method thereof | |
| CN107069020A (en) | A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode | |
| CN103227056B (en) | The preparation method of LiFePO4/expanded graphite combination electrode material and use the preparation method of lithium-ion capacitor of this material | |
| CN108780919A (en) | All solid state lithium-sulfur cell and its manufacturing method | |
| CN110299515A (en) | A kind of positive electrode active materials and preparation method thereof, Anode and battery | |
| CN105261742B (en) | A kind of sulphur system semisolid lithium battery and preparation method thereof | |
| CN100503451C (en) | Positive electrode material Li(1+X)V3O8 of Li-ion battery preparing process | |
| CN110835104A (en) | Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery | |
| CN107069079A (en) | A kind of solid state electrolyte and its preparation and application | |
| WO2021042987A1 (en) | Positive electrode active material, preparation method therefor, positive electrode sheet, lithium ion secondary battery, and battery module, battery pack and device containing lithium ion secondary battery | |
| CN105470518A (en) | Lithium sulfur battery sulfur cathode slurry and preparation method thereof, preparation method of lithium sulfur battery | |
| CN105226267B (en) | Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application | |
| CN104051720B (en) | A kind of material and its preparation and lithium ion anode active material, positive electrode, anode and battery containing the material | |
| CN101913655A (en) | Method for preparing lithium manganate cathode material by microwave sintering | |
| CN109004220A (en) | A kind of boronic acid compounds modification lithium ion battery silicium cathode and preparation method thereof | |
| CN103928659A (en) | Rechargeable battery | |
| CN109671912A (en) | A kind of fast charging type anode plate for lithium ionic cell preparation method | |
| CN109254036A (en) | A kind of electrochemical evaluation method of electrode material rapid charging performance | |
| CN108110234B (en) | Conductive polymer hydrogel and preparation method and application thereof | |
| CN110265626A (en) | Positive pole piece, preparation method thereof and lithium ion secondary battery | |
| CN104600242B (en) | A kind of lithium ion battery composite cathode material, anode pole piece and lithium ion battery | |
| CN110265622A (en) | Positive electrode plate and lithium ion secondary battery | |
| CN102683698B (en) | Preparation method of conductive modified lithium iron phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181127 |