CN105914371A - Phenolic resin-based hard carbon microspheres, preparation method thereof, negative electrode material and secondary battery - Google Patents
Phenolic resin-based hard carbon microspheres, preparation method thereof, negative electrode material and secondary battery Download PDFInfo
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- CN105914371A CN105914371A CN201610297381.3A CN201610297381A CN105914371A CN 105914371 A CN105914371 A CN 105914371A CN 201610297381 A CN201610297381 A CN 201610297381A CN 105914371 A CN105914371 A CN 105914371A
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- phenolic resin
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of secondary batteries, in particular to phenolic resin-based hard carbon microspheres, a preparation method thereof, and a negative electrode material containing the microspheres. The phenolic resin-based hard carbon microspheres provided by the invention are spherical; d002 is 0.375 to 0.380 nm; the specific surface area is 70 to 350 m<2>/g; the pore volume is 0.08 to 0.18 cm<3>/g. The phenolic resin-based hard carbon microspheres provided by the invention have a small specific surface area, structural stability, large interlayer spacing and rich pore structures, and can be applied to the negative electrode material of a lithium-ion battery or a sodium-ion battery, so that the battery has high capacity and stable cycle performance.
Description
Technical field
The application relates to secondary cell field, specifically, relating to a kind of phenolic resin base hard carbon microsphere,
Its preparation method and containing the negative material of this microsphere and secondary cell.
Background technology
Lithium ion battery cathode material is subject to wide along with the fast development of power lithium-ion battery
General concern.The capacity of traditional cathode material for lithium-ion power battery is low, cycle performance and multiplying power
Performance is the most poor and there is safety problem.
Graphite-like carbon negative pole material has that electrode potential is low, have extended cycle life, safety is good and price is low
The advantage such as honest and clean, becomes the main negative material of current commercial Li-ion battery.But graphite negative electrodes material
Material is due to its layer structure, and the compatibility with electrolyte is poor, easily occurs molten during discharge and recharge
Agent ion embeds altogether and causes structural deterioration, thus affects cyclical stability and the storehouse of graphite cathode material
Logical sequence efficiency, especially reduces the high rate performance of graphite cathode material, it is impossible to meet large-sized power battery
Required lasting large current discharging capability etc..With graphite-phase ratio, hard carbon has isotropic structure
Feature, interlamellar spacing is relatively big, can accelerate lithium ion diffusion, meanwhile, hard carbon material cycle performance and multiplying power
The feature such as better performances, low cost so that it is again by people's in terms of power-type lithium ion battery
Pay close attention to.
In order to improve the electrical property of hard carbon microsphere, special proposition the application.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of phenolic resin base hard carbon microsphere.
Second goal of the invention of the application is to propose the preparation method of this phenolic resin base hard carbon microsphere.
3rd goal of the invention of the application is to propose the negative pole containing this phenolic resin base hard carbon microsphere
Material.
4th goal of the invention of the application is to propose the secondary cell containing this negative material.
In order to complete the purpose of the application, the technical scheme of employing is:
The application relates to a kind of phenolic resin base hard carbon microsphere, and described phenolic resin base hard carbon microsphere is ball
Shape, the d of described phenolic resin base hard carbon microsphere002It is 0.375～0.380nm.
Preferably, the specific surface area of described phenolic resin base hard carbon microsphere is 70～350m2/ g, hole body
Amass is 0.08～0.18cm3/g。
Preferably, the particle diameter of described phenolic resin base hard carbon microsphere is 1～10 μm.
The application further relates to the preparation method of this phenolic resin base hard carbon microsphere, at least includes following step
Rapid:
(1) synthesis thermosetting phenolic resin solution；
(2) described thermosetting phenolic resin solution is diluted to the aqueous solution that concentration is 5～15wt%,
It is preferably 8～12wt%；Described aqueous solution is incubated under the conditions of 180～230 DEG C 5～8h and carries out water
Thermal response；
(3), after cooling, the solution that hydro-thermal reaction obtains is centrifuged process, and to obtain phenolic resin micro-
Ball, described phenolic resin microspheres drying obtains novolak resin precursor body；
(4) the novolak resin precursor body prepared is carried out carbonization in an inert atmosphere, obtain institute
State phenolic resin base hard carbon microsphere.
Preferably, described aqueous solution is poured in politef reactor, then by described polytetrafluoro
Ethylene reaction still is put in rustless steel water heating kettle and seals, and is then placed in all by described rustless steel water heating kettle
Phase reactor carries out hydro-thermal reaction.
Preferably, described centrifugal rotating speed is 2000～3000r/min.
Preferably, the condition of described carbonization be with the heating rate of 3～5 DEG C/min be warming up to 800～
1500 DEG C, it is incubated 2～5 hours.
The application further relates to a kind of negative material, contains the phenolic resin base of the application in this negative material
Hard carbon microsphere.
The application further relates to a kind of secondary cell, including anode pole piece, cathode pole piece, be arranged at described
Barrier film between positive pole and described negative pole, and electrolyte, described cathode pole piece includes negative current collector
With the negative material being arranged on described negative current collector, described negative material is the negative pole material of the application
Material.
Preferably, described secondary cell is lithium ion battery or sodium-ion battery.
The technical scheme of the application at least has a following beneficial effect:
The phenolic resin base hard carbon micro-sphere material of the application has low specific surface area and structural stability,
When application is for the negative material of lithium/sodium-ion battery, its spherical laminated structure be conducive to sodium ion or lithium from
Son embeds from all directions and abjection.
The phenolic resin base hard carbon micro-sphere material of the application has big interlamellar spacing and abundant pore structure,
More storage lithium or storage sodium space are provided, there is high capacity and stable cycle performance；Can apply to
Lithium ion battery or anode material of lithium-ion battery.
The hard carbon productivity obtained after the pyrolysis of the phenolic resin base hard carbon micro-sphere material of the application is high, and
Relative to other resin material raw material more horn of plenty, price is more cheap, it is possible to decrease product cost.
The preparation technology of the application is simple, easy to operate.
Accompanying drawing explanation
Fig. 1 is the phenolic resin hard carbon microsphere scanning electron microscope (SEM) photograph of the application；
Fig. 2 is the high rate performance figure of lithium ion battery 1#；
Fig. 3 is the cycle performance figure of lithium ion battery 1#；
Fig. 4 is the high rate performance figure of sodium-ion battery 6#；
Fig. 5 is the cycle performance figure of sodium-ion battery 6#.
Below in conjunction with specific embodiment, the application is expanded on further.Should be understood that these embodiments are only used
In explanation the application rather than restriction scope of the present application.
Detailed description of the invention
Present applicant proposes a kind of phenolic resin base hard carbon micro-sphere material, it has big interlamellar spacing and rich
Rich pore structure, can apply to lithium ion battery or anode material of lithium-ion battery so that battery specific volume
Amount height, multiplying power and cycle performance are excellent.
The phenolic resin base hard carbon microsphere of the application has perfect spherical structure, and smooth surface.
Implication spherical in the application refers to, on the centre of sphere of the phenolic resin base hard carbon microsphere of the application to sphere
The distance of any point is identical.The photo of its scanning electron microscope is as shown in Figure 1.
The d of the phenolic resin base hard carbon microsphere of the application002Being 0.375～0.380nm, it has big
Interlamellar spacing.Wherein d002Represent the average layer interlamellar spacing of graphite-like crystallite.
As a kind of improvement of the application phenolic resin base hard carbon microsphere, phenolic resin base hard carbon microsphere
Specific surface area is 70～350m2/ g, preferably 150～250m2/g；Pore volume be 0.08～
0.18cm3/ g, preferably 0.08～0.15cm3/g。
As a kind of improvement of the application phenolic resin base hard carbon microsphere, phenolic resin base hard carbon microsphere
Particle diameter is 1～10 μm.Particle diameter in the application is the median particle diameter of phenolic resin base hard carbon microsphere.
The application further relates to the preparation method of this phenolic resin base hard carbon microsphere, at least includes following step
Rapid:
(1) synthesis thermosetting phenolic resin solution；
(2) described thermosetting phenolic resin solution is diluted to the aqueous solution that concentration is 5～15wt%, will
Described aqueous solution is incubated 5～8h under the conditions of 180～230 DEG C and carries out hydro-thermal reaction；
(3), after reactor cooling, it is centrifuged reaction solution processing acquisition phenolic resin microspheres, is dried
Obtain novolak resin precursor body；
(4) the novolak resin precursor body prepared is carried out carbonization in an inert atmosphere, obtain described phenol
Urea formaldehyde base hard carbon microsphere.
As a kind of improvement of the application preparation method, in step (1), thermosetting phenolic resin
The synthetic method of solution comprises the following steps: phenol carries out addition with formaldehyde anti-in the basic conditions
Should, the condition of additive reaction is: constant temperature insulation 30～90min under 50～100 DEG C of temperature conditionss；
It is subsequently adding formalin, is warming up to 90～120 DEG C and continues reaction 50～100 minutes.
As a kind of improvement of the application preparation method, alkalescence condition is by adding alkaline aqueous solution, alkali
Property compound is selected from NaOH, KOH etc., and the concentration of alkaline aqueous solution is 1mol/L；Add alkali
The pH value of rear system is 3.0～5.0, preferably 3.5～4.5.
As a kind of improvement of the application preparation method, phenol and formaldehyde react first in both ratio
For 1:1～1:3, it is 1:1～1:4 that second time adds the ratio of formaldehyde.
As a kind of improvement of the application preparation method, in step (2), aqueous solution is poured into poly-
In tetrafluoroethene reactor, then described politef reactor is put in rustless steel water heating kettle also
Seal, politef reactor is placed in homogeneous reactor and carries out hydro-thermal reaction.
As a kind of improvement of the application preparation method, in step (2), thermosetting phenolic resin
The concentration of aqueous solution is 8～12wt%, and the concentration of aqueous solution can affect phenolic resin base hard carbon microsphere
Pattern and particle diameter, in the range of the aqueous solution of the application, can form sphericity good, smooth surface,
Particle diameter is at the hard carbon microsphere of 1～10 μm.
As a kind of improvement of the application preparation method, in step (3), centrifugal rotating speed be 2000～
3000r/min, centrifugal rotational speed affects the particle diameter of phenolic resin base hard carbon microsphere.
As a kind of improvement of the application preparation method, in step (3), the bar being dried after being centrifuged
Part is: be vacuum dried 3～24h at 60～100 DEG C.
As a kind of improvement of the application preparation method, in step (4), the heating curve of carbonization
It is that the heating rate of 3～5 DEG C/min is warming up to 800～1500 DEG C, is incubated 2～5 hours.Carbonization temperature
Degree has considerable influence to specific surface area and pore volume.
As a kind of improvement of the application preparation method, in step (4), the preferred nitrogen of inert atmosphere
Gas.
The application further relates to a kind of negative material, contains the phenolic resin base of the application in this negative material
Hard carbon microsphere.
As a kind of improvement of the application secondary battery cathode material, negative material is made by the following method
Standby: hard carbon microsphere, bonding agent, conductive agent to be mixed with the ratio of 7～8.5:2～0.5:1 and sizes mixing
After be coated on Copper Foil, in 100～120 DEG C vacuum drying 8～14h after, with the pressure pressure of 1MPa
After making type, it is prepared as negative electricity pole piece through punching.
The application further relates to a kind of secondary cell, and it includes anode pole piece, cathode pole piece, is arranged at institute
State the barrier film between positive pole and described negative pole, and electrolyte, cathode pole piece include negative current collector and
The negative material being arranged on negative current collector, negative material is the negative material of the application.
As a kind of improvement of the application secondary cell, when secondary cell is lithium ion battery, to electricity
Pole uses lithium metal, and electrolyte lithium salt comprises LiClO4Or LiPF6, reversible lithium storage gram volume be 250～
400mAh/g；When secondary cell is sodium-ion battery, electrode is used metallic sodium, electrolyte sodium
Salt comprises NaPF6Or NaClO4, reversible storage sodium gram volume is 200～320mAh/g.
As a kind of improvement of the application secondary cell, when secondary cell is lithium ion battery, first
Efficiency for charge-discharge can reach 65～75%, and capability retention is 85%, has good multiplying power and circulation
Performance.When secondary cell is sodium-ion battery, first charge-discharge efficiency is 60～70%, and capacity is protected
Holdup is 85%, and high rate during charging-discharging and cycle performance are good.
Embodiment 1
1, synthesis thermosetting phenolic resin solution: phenol and formaldehyde are separately added in there-necked flask, adds
After a small amount of NaOH aqueous solution, after addition alkali, the pH value of system is 4.0.Constant temperature 80 DEG C holding
60min；Being warming up to 100 DEG C after again adding formalin, reaction continues to keep 90 minutes, stops
Only reaction；During phenol and formaldehyde react first, both ratio is 1:1, and second time adds formaldehyde
Ratio be 1:1；
2, thermosetting phenolic resin solution is diluted to certain density aqueous solution, aqueous solution is poured into poly-four
In fluorothene reactor, then politef reactor is put in rustless steel water heating kettle and close
Envelope, carries out hydro-thermal reaction in homogeneous reactor, and the condition of hydro-thermal reaction is as shown in table 1；
3, after reactor cooling, it is centrifuged reaction solution processing acquisition phenolic resin microspheres, is centrifuged and turns
Speed is as shown in table 1；Then at 80 DEG C, it is vacuum dried 8h, obtains novolak resin precursor body；
4, by the novolak resin precursor body for preparing in nitrogen atmosphere, the actual conditions of heating curve is such as
Shown in table 1, obtain described phenolic resin base hard carbon microsphere.
Table 1
The physical property of the phenolic resin base hard carbon microsphere prepared is detected.Wherein, d002
Being composed by the XRD figure of phenolic resin base hard carbon microsphere utilizes Bragg equation to be calculated；Specific surface area
Obtained by BET specific surface area algoscopy measurement.Wherein, carburizing temperature is to specific surface area and hole body
Long-pending impact is maximum, and the impact of other parameters is less.With the rising of carburizing temperature, d002First increase and subtract afterwards
Little, specific surface area and pore volume are gradually reduced, and wherein 1-1 (1250 DEG C of carbonization treatment) has maximum
Interlamellar spacing d002, more lithium/sodium ion can be stored.Testing result is as shown in table 2:
Table 2
| Numbering | d002(nm) | Specific surface area (m2/g) | Particle diameter is (μm) | Pore volume (cm3/g) |
| 1-1 | 0.389 | 250 | 1～10 | 0.13 |
| 1-2 | 0.378 | 350 | 1～10 | 0.18 |
| 1-3 | 0.386 | 290 | 1～10 | 0.15 |
| 1-4 | 0.380 | 200 | 1～10 | 0.12 |
| 1-5 | 0.375 | 70 | 1～10 | 0.08 |
Then phenolic resin base hard carbon microsphere is prepared lithium ion battery as negative material:
Concrete preparation method is: phenolic resin base hard carbon microsphere and bonding agent, the conduction that will prepare
Agent is coated on Copper Foil, in 100～120 DEG C of vacuum drying after sizing mixing with the ratio mixing of 8:1:1
After 10h, with the pressure of 1MPa compressing after, be prepared as cathode pole piece 1-1～1-5 through punching.
Using above-mentioned cathode pole piece 1-1～1-5 as the negative pole of lithium ion battery, lithium metal is to electrode,
Use the LiClO of 1M4Or LiPF6EC/DMC (Vol 1:1) solution be electrolyte solution,
Celgard2400 porous polypropylene film, as barrier film, is assembled in the glove box of full argon
CR2430 type button cell 1#～5#.
The performance of the lithium ion battery prepared is detected: test voltage excursion is
0.002～2.7V, the result that detection obtains is as shown in table 3.
High rate performance with the detection method of cycle performance is:
Table 3
Wherein, the high rate performance of battery 1# is with cycle performance as shown in Figures 4 and 5.With carburizing temperature
Raise, store up lithium gram volume first increases and then decreases, this and its interlamellar spacing d002Changing Pattern consistent, main
If big interlamellar spacing is conducive to the transmission of lithium ion, its dynamic performance is more preferable, perform better than times
Rate performance.In general, 1# battery core has the storage lithium performance of optimum.
Embodiment 2
Cathode pole piece 1-1～1-5 prepared in embodiment 1 is prepared respectively sodium-ion battery 6#～
10#, is metallic sodium to electrode, and electrolyte uses NaPF6Or NaClO4。
Using above-mentioned cathode pole piece 1-1～1-5 as the negative pole of sodium-ion battery, metallic sodium is to electrode,
Use the NaPF of 1M6Or NaClO4EC/DMC (Vol 1:1) solution be electrolyte solution,
Celgard2400 porous polypropylene film, as barrier film, is assembled in the glove box of full argon
CR2430 type button cell 6#～10#.
The performance of the sodium-ion battery prepared is detected: test voltage excursion is
0.002～2.7V, the result that detection obtains is as shown in table 4.It is consistent with the Changing Pattern of lithium ion battery,
With the rising of carburizing temperature, storage sodium gram volume is also first increases and then decreases, and 6# battery core has optimum
Storage sodium performance.
Table 4
Wherein, the high rate performance of battery 6# is with cycle performance as shown in Figures 4 and 5.
Although the application is open as above with preferred embodiment, but is not for limiting claim, appoint
What those skilled in the art, on the premise of conceiving without departing from the application, can make some possible
Variation and amendment, the scope that therefore protection domain of the application should be defined with the application claim
It is as the criterion.
Claims (10)
1. a phenolic resin base hard carbon microsphere, it is characterised in that described phenolic resin base hard carbon microsphere is
Spherical, the d of described phenolic resin base hard carbon microsphere002It is 0.375～0.380nm.
Phenolic resin base hard carbon microsphere the most according to claim 1, it is characterised in that described phenolic aldehyde
The specific surface area of resin base hard carbon microsphere is 70～350m2/ g, pore volume is 0.08～0.18m3/g。
Phenolic resin base hard carbon microsphere the most according to claim 1, it is characterised in that described phenolic aldehyde
The particle diameter of resin base hard carbon microsphere is 1～10 μm.
4. a preparation method for phenolic resin base hard carbon microsphere as claimed in claim 1, its feature exists
In, at least comprise the following steps:
(1) synthesis thermosetting phenolic resin solution；
(2) described thermosetting phenolic resin solution is diluted to the aqueous solution that concentration is 5～15wt%,
It is preferably 8～12wt%；Described aqueous solution is incubated under the conditions of 180～230 DEG C 5～
8h carries out hydro-thermal reaction；
(3), after cooling, the solution that hydro-thermal reaction obtains is centrifuged process, and to obtain phenolic resin micro-
Ball, described phenolic resin microspheres drying obtains novolak resin precursor body；
(4) the novolak resin precursor body prepared is carried out carbonization in an inert atmosphere, obtain described
Phenolic resin base hard carbon microsphere.
Preparation method the most according to claim 4, in step (2), pours into described aqueous solution
In politef reactor, then described politef reactor is put into rustless steel hydro-thermal
In still and seal, then described rustless steel water heating kettle is placed in homogeneous reactor to carry out hydro-thermal anti-
Should.
Preparation method the most according to claim 4, in step (3), described centrifugal rotating speed is
2000～3000r/min.
Preparation method the most according to claim 4, in step (4), the condition of described carbonization is
It is warming up to 800～1500 DEG C with the heating rate of 3～5 DEG C/min, is incubated 2～5 hours.
8. a negative material, it is characterised in that containing such as claim 1～7 in described negative material
Phenolic resin base hard carbon microsphere described in one claim.
9. a secondary cell, including anode pole piece, cathode pole piece, is arranged at described positive pole and described negative
Barrier film between pole, and electrolyte, described cathode pole piece includes negative current collector and is arranged at
Negative material on described negative current collector, it is characterised in that described negative material is such as right
Require the negative material described in 8.
Secondary cell the most according to claim 9, it is characterised in that described secondary cell is lithium
Ion battery or sodium-ion battery.
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