CN109616668A - The micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size - Google Patents
The micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size Download PDFInfo
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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 present invention relates to a kind of micro- preparation methods for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size, this method, which refers to for natural flake graphite to be added in sulfuric acid solution, to be stirred, and potassium permanganate is then added, successively in 20 ~ 40 DEG C of 2 ~ 4h of reaction, 40 ~ 60 DEG C of reactions 1 ~ 3h, 60 ~ 80 DEG C of 0.5 ~ 3h of reaction；After reaction, the natural graphite handled through filtering cleaning to pH=7 to get oxide etch；The natural graphite of oxide etch processing made annealing treatment after drying to get.Present invention process is simple, low in cost; the resulting micro- expansion layer natural graphite lithium cell negative pole product of manganese oxide-small size; high rate performance is excellent, and the production technology of prepare with scale may be implemented, and is expected to obtain lithium cell negative pole material products application as natural graphite product class high added value.
Description
Technical field
The present invention relates to technical field of lithium batteries more particularly to the lithium battery micro- expansion layers of negative electrode material manganese oxide-small size
The preparation method of natural graphite.
Background technique
With the continuous development of smart phone, tablet computer, portable power, uninterrupted power system and electric car, entirely
Demand of the ball to lithium ion battery is growing.Lithium ion battery negative material is the key factor for determining lithium electrical property, graphite
The advantages such as class carbon has charging/discharging voltage platform low as negative electrode material, and safety is good and cheap are current commercialization lithiums
The main material of ion battery.But when traditional natural graphite is as lithium cell negative pole material, it is molten that layer structure easily leads to electrolyte
The total insertion of agent ion, causes graphite laminate structural damage, and cyclical stability and coulombic efficiency is caused to be affected.Also,
The anisotropic structure feature of graphite limits the problems such as free diffusing of the lithium ion in graphite-structure, so as to cause its multiplying power
Performance is affected.
For natural graphite lithium ionic battery performance problems, the main means modified natural graphite using physics and chemistry,
Wherein physical method is mainly the broken free diffusing for reducing size and spheroidization increase lithium ion, and chemical method then includes expanding
Big interlamellar spacing, cladding and other compound substances etc. increase the transmission speed and hoist capacity of electrolyte.But still lack one
Kind is realized to stone simultaneously in combination with the modifying natural graphite technology of chemically and physically modified effect, simple low cost
The interlamellar spacing that is broken and expanding graphite of ink and meet the compound of other substances simultaneously.Therefore, develop a kind of inexpensive, simple
And there is the preparation method for taking into account the excellent properties graphite lithium cell negative pole material that various improvement techniques are integrated important reality to answer
Use meaning.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of simple processes, low-cost lithium battery negative electrode material
The micro- preparation method for expanding layer natural graphite of manganese oxide-small size.
To solve the above problems, the micro- expansion layer natural graphite of lithium cell negative pole material manganese oxide-small size of the present invention
Preparation method, it is characterised in that: by natural flake graphite be added 50 ~ 80wt% sulfuric acid solution in 10 ~ 25 DEG C of stirring 30min ~
Then potassium permanganate is added in 5h, successively in 20 ~ 40 DEG C of reactions 2 ~ 4h, 40 ~ 60 DEG C of reactions 1 ~ 3h, 60 ~ 80 DEG C of 0.5 ~ 3h of reaction；
After reaction, the natural graphite handled through filtering cleaning to pH=7 to get oxide etch；The oxide etch is handled natural
Graphite made annealing treatment after drying to get；The matter of the natural flake graphite, the sulfuric acid solution and the potassium permanganate
Amount is than being 1:7:0.5 ~ 1:20:3.
The size of the natural flake graphite is 45 μm ~ 75 μm, and purity is 80wt% ~ 99wt%.
The mass ratio of the natural flake graphite, the sulfuric acid solution and the potassium permanganate is 1:7:0.5 ~ 1:20:3.
The stirring rate is 100 ~ 500rpm/min.
The drying condition refers to that temperature is 60 ~ 80 DEG C, and the time is 10 ~ 15h.
The annealing condition refers to that temperature is 500 ~ 800 DEG C, reaction speed is 5 DEG C/min, soaking time 30min
~4h。
Compared with the prior art, the present invention has the following advantages:
1, the present invention utilizes certain concentration sulphur using natural graphite, sulfuric acid and oxidant as raw material using synchronous etching oxidation technology
The strong corrosive of acid and the interaction of oxidant, chemical etching and broken reduction graphite size, improve lithium ion natural
The transmission speed of graphite layers, the inexpensive technical of this low cost realize the common work of the multiple groups equipment such as ball mill and crusher
Make completed graphite degree of crushing.
2, the present invention expands layer natural graphite, the official of natural graphite edge oxidation using the oxidation of potassium permanganate oxidant edge
The distance for becoming expanding interlayer while gas overflowing interlayer can be rolled into a ball, the transmission of electrolyte and the diffusion of ion are conducive to,
When improving natural graphite as negative electrode material, the lithium ion of solvation is inserted into volume expansion caused by graphite layers process,
And graphite linings collapse caused by cycle performance the problems such as deteriorating, and the annealed processing of excessive potassium permanganate oxidant converts
For the load of manganese oxide, the lithium capacitance and high rate performance of natural graphite are further improved.
3, the present invention is raw material instead of biography using chemical reaction kettle and the certain concentration sulfuric acid and oxidant of cheap and simple
The industrial crusher of system, and solve the problems, such as purification caused by broken yield and post-process, save equipment investment 1/8
The cost of cost and energy consumption investment 1/10.
4, the temperature made annealing treatment in the present invention is at 800 DEG C hereinafter, and cladding and high temperature cabonization without carrying out the later period
Processing, has saved energy consumption and production cost.
5, the synchronous oxidation intercalation and by-product manganese oxide to graphite for combining sulfuric acid and potassium permanganate of the present invention
Coordination enhancing, save and raw material advantage be utilized, improve the battery performance of material jointly.
6, the micro- expansion layer natural graphite lithium cell negative pole product of manganese oxide-small size that the present invention obtains, high rate performance is excellent, and
And the production technology of prepare with scale may be implemented, it is expected to obtain lithium cell negative pole material production as natural graphite product class high added value
Product application.
7, present invention process process is simple, manpower consumption is low, equipment investment is few.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is according to the stereoscan photograph for preparing modified natural graphite in embodiment 1.
Fig. 2 is the X ray diffracting data according to the modified natural graphite prepared in embodiment 1.
Fig. 3 is figure of the prepared modified natural graphite as ion cathode material lithium half-cell multiplying power property in embodiment 1.
Fig. 4 is to recycle under the prepared peace/gram current density of modified natural graphite lithium ionic negative electrode material 0.1 in embodiment 1
The figure of characteristic.
Fig. 5 is the stereoscan photograph according to the graphene microchip prepared in comparative example 1.
Fig. 6 is the stereoscan photograph according to the graphite flake prepared in comparative example 2.
Fig. 7 is modified natural graphite prepared in embodiment 3 as ion cathode material lithium half-cell multiplying power property
Figure.
Fig. 8 is to recycle under the prepared peace/gram current density of modified natural graphite lithium ionic negative electrode material 0.1 in embodiment 3
The figure of characteristic.
Specific embodiment
The micro- preparation method for expanding layer natural graphite of 1 lithium cell negative pole material manganese oxide of embodiment-small size, by 45 μm of 1g
Natural flake graphite, which is added in 10mL 65wt% sulfuric acid solution, stirs 2h in 25 DEG C of rates with 300rpm/min.Then 1g is added
Potassium permanganate powder, successively in 35 DEG C of reactions 2 h, 60 DEG C of reactions 1h, 80 DEG C of reaction 0.5h；It filters after reaction, through high-purity
Water cleans the natural graphite handled to pH=7 to get oxide etch.The natural graphite of oxide etch processing is in 60 DEG C of dry 10h
Afterwards, it is placed in magnetic boat, is sintered in tube furnace, nitrogen protection, condition is 5 DEG C/min, is warming up to 600 DEG C, protects at this temperature
Warm 2h is to get the micro- expansion layer natural graphite of lithium cell negative pole material manganese oxide-small size.
Gained modified graphite such as Fig. 1, graphite block are cracked into the photo of multiple graphite small blocks and in scanning electron microscopies
Amplify the photo of the manganese oxide particle found under the conditions of mirror.Fig. 2 is the XRD data of sample, which has manganese dioxide and natural
Graphite composition.Additionally will be seen that by EDS elemental analysis: after logical calcining, purity > 98wt% of sample is shown in Table 1.
Table 1
Fig. 3 is figure of the natural graphite of modification prepared in embodiment 1 as ion cathode material lithium half-cell multiplying power property.
Test method: using gained modified natural graphite as lithium ion battery electrode material assemble lithium ion half-cell: select lithium piece for
To electrode, it is dissolved in diethyl carbonate and with 1 MLiPF6 of diethyl carbonate as electrolyte, (water content is small in glove box
In 0.1 ppm, oxygen content is less than 0.3 ppm) after inner progress CR2032 half-cell assembling according to gradient current density (0.1 peace/
Gram, 0.3 peace/gram, 0.5 peace/gram, 0.8 peace/gram, 1 peace/gram, 2 peace/gram, 3 peace/gram) test.
Fig. 4 be in embodiment 1 prepared modified natural graphite as lithium ion battery electrode material in 0.1 peace/gram electric current
The figure of cycle characteristics under density.Test method: for battery assembly method with battery assembly technique in Fig. 3, testing current density is 0.1
Peace/gram.
Comparative example 1 the difference from embodiment 1 is that sulfuric acid concentration selection 98% concentrated sulfuric acid other conditions it is identical,
Specific step is as follows:
2h, speed of agitator 300rpm/ are stirred in the aqueous sulfuric acid of 10mL98wt% using 45 μm of natural flake graphites of 1g
Min, reaction temperature are 25 DEG C.1g potassium permanganate powder is added later, continues to stir 2h at 35 DEG C, in 60 DEG C of reaction 1h,
80 DEG C of reaction 0.5h, after the reaction was completed, the dioxygen water process that 1mL 30wt% is added is the potassium permanganate of reaction, after reaction,
Sample is filtered, recycling reaction liquid can be recycled, and cleaning to pH=7 with high purity water later terminates, and sample is 60
It is dry in DEG C baking oven.It takes whole samples to be placed in magnetic boat, is sintered in tube furnace, nitrogen protection, condition is 5 DEG C/min, heating
To 600 DEG C, 2h is kept the temperature at this temperature, obtains sample.Gained sample such as Fig. 5, as can be seen from the figure without going out current embodiment 1
Spherical graphite and microdilatancy graphite in Fig. 1, the sulfuric acid of high concentration more have oxidisability, and etching and corrosivity are insufficient, obtain
Sample be graphene microchip.
Comparative example 2 the difference from embodiment 1 is that sulfuric acid concentration selection 30% alkene sulfuric acid other conditions it is identical,
Specific step is as follows:
2h, speed of agitator 300rpm/ are stirred in the aqueous sulfuric acid of 10mL 30wt% using 45 μm of natural flake graphites of 1g
Min, reaction temperature are 25 DEG C.1g potassium permanganate powder is added later, continues to stir 2h at 35 DEG C, in 60 DEG C of reaction 1h,
80 DEG C are reacted 30 minutes, and after the reaction was completed, the dioxygen water process that 1mL 30wt% is added is the potassium permanganate of reaction, and reaction terminates
Afterwards, sample is filtered, recycling reaction liquid can be recycled, and cleaning to pH=7 with high purity water later terminates, sample
It is dry in 60 DEG C of baking ovens.It taking whole samples to be placed in magnetic boat, is sintered in tube furnace, nitrogen protection, condition is 5 DEG C/min,
600 DEG C are warming up to, keeps the temperature 2h at this temperature, obtains sample.Gained sample such as Fig. 6, as can be seen from the figure without going out reality
The spherical graphite and microdilatancy graphite in 1 Fig. 1 of example are applied, for alkene sulfuric acid also without enough etchings and corrosion, obtained sample is stone
Ink sheet.
The micro- preparation method for expanding layer natural graphite of 2 lithium cell negative pole material manganese oxide of embodiment-small size, by 48 μm of 1g
Natural flake graphite, which is added in 20mL 60wt% sulfuric acid solution, stirs 1h in 25 DEG C of rates with 300rpm/min.Then 2g is added
Potassium permanganate, successively in 35 DEG C of reactions 2h, 45 DEG C of reactions 2h, 75 DEG C of reaction 1h；It filters, is cleaned through high purity water after reaction
The natural graphite handled to pH=7 to get oxide etch.The natural graphite of oxide etch processing is placed in after 60 DEG C of dry 15h
It in magnetic boat, is sintered in tube furnace, nitrogen protection, condition is 5 DEG C/min, is warming up to 500 DEG C, keeps the temperature 1h at this temperature, i.e.,
Obtain the micro- expansion layer natural graphite of lithium cell negative pole material manganese oxide-small size.
The micro- preparation method for expanding layer natural graphite of 3 lithium cell negative pole material manganese oxide of embodiment-small size, by 45 μm of 1g
Natural flake graphite, which is added in 10mL 60wt% sulfuric acid solution, stirs 30min in 10 DEG C of rates with 300rpm/min.Then plus
Enter 3g potassium permanganate, successively in 35 DEG C of reactions 4h, 50 DEG C of reactions 1h, 60 DEG C of reaction 1h；It filters after reaction, through high purity water
Clean the natural graphite handled to pH=7 to get oxide etch.Oxide etch processing natural graphite after 60 DEG C of dry 12h,
It is placed in magnetic boat, is sintered in tube furnace, nitrogen protection, condition is 5 DEG C/min, is warming up to 800 DEG C, keeps the temperature at this temperature
1h is to get the micro- expansion layer natural graphite of lithium cell negative pole material manganese oxide-small size.
Fig. 8 is the natural graphite of modification prepared in embodiment 3 as ion cathode material lithium half-cell multiplying power property
Figure.Test method: lithium ion half-cell is assembled using gained modified natural graphite as lithium ion battery electrode material: selection lithium
Piece is to be dissolved in diethyl carbonate and with 1 MLiPF6 of diethyl carbonate as electrolyte, (water contains in glove box to electrode
Amount is less than 0.1 ppm, and oxygen content is less than 0.3 ppm) after inner progress CR2032 half-cell assembling according to gradient current density (0.1
Peace/gram, 0.3 peace/gram, 0.5 peace/gram, 0.8 peace/gram, 1 peace/gram, 2 peace/gram, 3 peace/gram) test.
Fig. 8 be in embodiment 3 prepared modified natural graphite as lithium ion battery electrode material in 0.1 peace/gram electric current
The figure of cycle characteristics under density.Test method: battery assembly method tests current density with battery assembly technique described in Fig. 3
For 0.1 peace/gram.
The micro- preparation method for expanding layer natural graphite of 4 lithium cell negative pole material manganese oxide of embodiment-small size, by 75 μm of 1g
Natural flake graphite, which is added in 20mL 50wt% sulfuric acid solution, stirs 30min in 10 DEG C of rates with 300rpm/min.Then plus
Enter 3g potassium permanganate, successively in 35 DEG C of reactions 4h, 50 DEG C of reactions 1h, 60 DEG C of reaction 1h；It filters after reaction, through with 100mL
The hydrochloric acid water of 5wt% repeatedly rinses sample removal Mn ion, is later cleaned with high purity water and to be handled to pH=7 to get oxide etch
Natural graphite.The natural graphite of oxide etch processing is placed in magnetic boat, is sintered in tube furnace after 60 DEG C of dry 13h, nitrogen
Protection, condition are 5 DEG C/min, are warming up to 800 DEG C, keep the temperature 1h at this temperature to get lithium cell negative pole material manganese oxide-small size
Micro- expansion layer natural graphite.
The micro- preparation method for expanding layer natural graphite of 5 lithium cell negative pole material manganese oxide of embodiment-small size, by 50 μm of 1g
Natural flake graphite, which is added in 20mL 80wt% sulfuric acid solution, stirs 5h in 15 DEG C of rates with 100rpm/min, is then added 3
G potassium permanganate, successively in 20 DEG C of reactions 3.5h, 40 DEG C of reactions 3h, 60 DEG C of reaction 3h；It filters after reaction, it is clear through high purity water
It is washed till the natural graphite that pH=7 are handled to get oxide etch.The natural graphite of oxide etch processing is set after 80 DEG C of dry 10h
It in magnetic boat, is sintered in tube furnace, nitrogen protection, condition is 5 DEG C/min, is warming up to 700 DEG C, keeps the temperature at this temperature
0.5h is to get the micro- expansion layer natural graphite of lithium cell negative pole material manganese oxide-small size.
The micro- preparation method for expanding layer natural graphite of 6 lithium cell negative pole material manganese oxide of embodiment-small size, by 60 μm of 1g
Natural flake graphite, which is added in 7mL 70wt% sulfuric acid solution, stirs 30min in 15 DEG C of rates with 500rpm/min, is then added
0.5g potassium permanganate, successively in 40 DEG C of reactions 2h, 50 DEG C of reactions 2h, 70 DEG C of reaction 2h；It filters after reaction, through high purity water
Clean the natural graphite handled to pH=7 to get oxide etch.Oxide etch processing natural graphite after 70 DEG C of dry 10h,
It is placed in magnetic boat, is sintered in tube furnace, nitrogen protection, condition is 5 DEG C/min, is warming up to 700 DEG C, keeps the temperature at this temperature
4h is to get the micro- expansion layer natural graphite of lithium cell negative pole material manganese oxide-small size.
In above-described embodiment 1 ~ 6, the purity of natural flake graphite is 80wt% ~ 99wt%.
Claims (6)
1. the micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size, it is characterised in that: by natural scale
Graphite is added in 50 ~ 80wt% sulfuric acid solution in 10 ~ 25 DEG C of stirring 30min ~ 5h, potassium permanganate is then added, successively in 20 ~ 40
DEG C reaction 2 ~ 4h, 40 ~ 60 DEG C of reactions 1 ~ 3h, 60 ~ 80 DEG C of 0.5 ~ 3h of reaction；After reaction, through suction filtration cleaning to pH=7, i.e.,
Obtain the natural graphite of oxide etch processing；The natural graphite of oxide etch processing made annealing treatment after drying to get；
The mass ratio of the natural flake graphite, the sulfuric acid solution and the potassium permanganate is 1:7:0.5 ~ 1:20:3.
2. the micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size as described in claim 1, special
Sign is: the size of the natural flake graphite is 45 μm ~ 75 μm, and purity is 80wt% ~ 99wt%.
3. the micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size as described in claim 1, special
Sign is: the mass ratio of the natural flake graphite, the sulfuric acid solution and the potassium permanganate is 1:7:0.5 ~ 1:20:3.
4. the micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size as described in claim 1, special
Sign is: the stirring rate is 100 ~ 500rpm/min.
5. the micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size as described in claim 1, special
Sign is: the drying condition refers to that temperature is 60 ~ 80 DEG C, and the time is 10 ~ 15h.
6. the micro- preparation method for expanding layer natural graphite of lithium cell negative pole material manganese oxide-small size as described in claim 1, special
Sign is: the annealing condition refer to temperature be 500 ~ 800 DEG C, reaction speed is 5 DEG C/min, soaking time be 30min ~
4h。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112374552A (en) * | 2020-11-12 | 2021-02-19 | 昆明云大新能源有限公司 | Composite modified graphite negative electrode material and preparation method thereof |
| CN113363447A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Hard carbon composite graphite negative electrode material and preparation method thereof |
| CN113363448A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Soft carbon composite graphite negative electrode material and preparation method thereof |
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| CN113363448A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Soft carbon composite graphite negative electrode material and preparation method thereof |
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Application publication date: 20190412 |