CN108242538A - A kind of preparation method of hollow sandwich type iron-based negative material - Google Patents
A kind of preparation method of hollow sandwich type iron-based negative material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of hollow sandwich type iron-based negative material, it includes the following steps：（a）Sulphonated polymers microballoon or fiber are distributed to containing Fe3+Aqueous solution in, heating reaction, dry the first nucleocapsid compound；（b）The first nucleocapsid compound is dispersed in the buffered aqueous solution containing trishydroxymethylaminomethane, add in dopamine under agitation and it is made to obtain sandwich type polymer composites in the first nucleocapsid composite surface progress polymerisation；（c）The sandwich type polymer composites and sulphur source, selenium source or phosphorus source with volatilization property are calcined in inert gas atmosphere.With simple for process, at low cost, easily-controlled experimental conditions, the feature being easy to implement；Used chemical reagent has hypotoxicity, and serious burden will not be caused to environment.
Description
Technical field
The invention belongs to lithium cell cathode material fields, are related to a kind of preparation method of negative material, and in particular to a kind of
The preparation method of hollow sandwich type iron-based negative material.
Background technology
As one of most promising electrical energy storage, lithium ion battery has been developed that alleviate the energy and ring
The challenge that border is brought.At present, commercialized lithium ion battery negative material has fabulous usually using carbon-based material, carbon-based material
Cyclical stability, but since its theoretical specific capacity is relatively low, so as to strongly limit the raising of its performance and application field.
Therefore, novel high performance lithium ionic cell cathode material is developed, is of great significance to the promotion of performance of lithium ion battery.
In numerous lithium ion battery negative materials, iron-based (such as oxide, sulfide and selenides) nano material is relatively low due to its
Cost, environmental-friendly characteristic and higher theoretical specific capacity etc. by researcher extensive concern.Nevertheless, these are high theoretical
The negative material of capacity is in practical research and application, and but there is urgent need to solve the problems：(1) in charge and discharge repeatedly
Cheng Zhonghui is along with huge volume deformation, these deformation can cause active material to crush and lose electrical contact, so as to cause following
The capacity of ring process in which materials drastically declines, and cannot get satisfactory cyclical stability；(2) compared with Carbon anode, these are negative
The conductivity of pole material is poor, further improves so as to influence chemical property.Therefore, how to design and prepare high power capacity,
The iron-based negative electrode of lithium ion battery of stable cycle performance is the key that realize that it is applied in practice.
Improve iron-based negative electrode of lithium ion battery chemical property be always negative material research emphasis, common strategy
Mainly there is two categories below.First, iron-based negative material is prepared into the nano material with different-shape structure such as cube, ball
Shape, threadiness, petal-shaped etc., stress caused by adapt to volume change.The characteristics of these nanostructureds are main has with higher
Specific surface area, enter the approach of active material so as to increase lithium ion and shorten lithium ion transport approach, increase is quickly filled
Discharge capability.Simultaneously as the smaller size of nano material, improves the carrying capacity strained to lithium ion deintercalation, Jin Ergai
Into charge and discharge circulation life.Second, the carbon progress higher with conductivity of iron-based negative material is compound, it gives full play to therebetween
Synergistic effect during lithium ion storage.First, in the combination electrode material of this iron-based material and carbon, carbon have compared with
Good electron transport ability can dramatically improve the electric conductivity of iron-based material, improve the utilization rate of iron-based material and obtain compared with
High lithium storage content.Secondly, volume change very little of the carbon material in lithium ion charge and discharge process, and then iron-based material can be buffered
Expect huge volume change, iron-based material is prevented to reunite and crush, to promote the cyclical stability of iron-based negative material.However,
Although carbon-coating can improve the physical property of iron-based material core, improve it is limited, especially for the iron-based material of large-size
The performance boost of core is extremely limited.Therefore, develop a kind of simple, effective and pervasive iron-based anode material for preparing
Method is very urgent.
Invention content
A kind of hollow sandwich type iron-based negative material is provided the invention aims to overcome the deficiencies in the prior art
Preparation method.
In order to achieve the above objectives, the technical solution adopted by the present invention is：A kind of hollow sandwich type iron-based negative material
Preparation method, it includes the following steps：
(a) sulphonated polymers microballoon or fiber are distributed to containing Fe3+Aqueous solution in, heating reaction, dry the
One nucleocapsid compound；
(b) the first nucleocapsid compound is dispersed in the buffered aqueous solution containing trishydroxymethylaminomethane, stirred
Dopamine is added under the conditions of mixing and it is made to carry out polymerisation in the first nucleocapsid composite surface and obtains sandwich type polymerization again
Close object；
(c) by the sandwich type polymer composites calcined in inert gas atmosphere or with waving
Sulphur source, selenium source or the phosphorus source of hair property are calcined in inert gas atmosphere.
Optimally, in step (a), the sulphonated polymers microballoon is sulphonated polystyrene microballoon, described sulfonated
Polymer fiber is sulfonated poly- divinylbenzene fiber.
Further, a diameter of 200~700nm of the sulphonated polymers microballoon, the sulfonated polymeric fibres
A diameter of 20~100nm.
Optimally, it is described to contain Fe in step (a)3+Aqueous solution by into water add source of iron be formulated, the iron
Source is the mixture of one or more compositions in ferric nitrate, iron chloride and ferric sulfate.
Optimally, in step (a), the heating temperature is 60~90 DEG C；It is centrifuged after reaction, successively with water, ethyl alcohol
Washing is placed in baking oven dry.
Optimally, in step (c), the sulphur source is sulphur powder, and the selenium source is selenium powder, and phosphorus source is sodium hypophosphite.
Further, in step (c), the calcination temperature is 500~700 DEG C, calcination time is 1~5 hour
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：The hollow Sanming City of the present invention
The preparation method of sections base negative material is controlled, by the compound ferro element of sulphonated polymers microparticle surfaces, then compound poly- DOPA
Amine can form the double carbon-coating sandwich structures for being sandwiched between iron compound after calcining in this way, not only conducive to electronics and ion
Conduction, and the diffusion path of lithium ion can be shortened, the contact area of material and electrolyte is increased, so as to greatly improve
The electrochemical kinetics of material；And dopamine material is finally derived as carbon-coating, which is not only conducive to improve the electricity of electrode material
Conductance, and can be with stabilized electrodes material in electrochemical process structural stability, and obtain the excellent electricity of cyclical stability
Chemical property；The technique that whole preparation process is related to only is low temperature heating water bath, centrifugation, drying, calcining etc., has technique letter
Single, at low cost, easily-controlled experimental conditions, the feature being easy to implement；Used chemical reagent has hypotoxicity, to environment not
It can cause serious burden.
Description of the drawings
It in the present invention with sulphonated polystyrene microballoon (SPS) is that template prepares hollow " sandwich type " structure that attached drawing 1, which is,
The flow diagram of iron-based lithium ion battery negative material；
Attached drawing 2 is the SEM using SPS as hollow " sandwich type " the structure iron base composite material obtained by template in the present invention
Figure：(a) embodiment 1, (b) embodiment 2, (c) embodiment 8；
Attached drawing 3 is using SPNF as hollow " sandwich type " the structure iron-based anode material obtained by template in the present invention
SEM figure：(a) embodiment 3, (b) embodiment 4, (c) embodiment 9；
Attached drawing 4 is hollow " sandwich type " the structure iron-based anode material EDX characterization results obtained by the present invention：a)
Embodiment 1, b) embodiment 2, c) embodiment 8；D) embodiment 3, e) embodiment 4, f) embodiment 9；
Attached drawing 5 is the X-ray diffraction spectrum of iron-based anode material in embodiment 1-4, embodiment 8-9；
Attached drawing 6 is C@FeS obtained in embodiment 12The chemical property curve of@C-materials：A) high rate performance, b) cycle
Performance, c) CV curves, d) charging and discharging curve；
Attached drawing 7 is the chemical property curve of C@FeSe@C-materials obtained in embodiment 2：A) multiplying power and cycle performance,
B) charging and discharging curve, c) CV curves；
Attached drawing 8 is C@Fe obtained in embodiment 83O4The chemical property curve of@C-materials：A) high rate performance, b) charge and discharge
Electric curve, c) CV curves, d) cycle performance.
Specific embodiment
The preparation method of the hollow sandwich type iron-based negative material of the present invention, it includes the following steps：It (a) will be sulfonated poly-
It closes object microballoon or fiber is distributed to containing Fe3+Aqueous solution in, heating reaction, dry the first nucleocapsid compound；(b) by described in
First nucleocapsid compound (i.e. sulfonated polymer@FeOOH) is dispersed in the buffered aqueous solution containing trishydroxymethylaminomethane,
Dopamine (DA) is added under stirring condition and it is made to carry out polymerisation in the first nucleocapsid composite surface and obtains sandwich type
Polymer composites (sulfonated polymer@FeOOH@PDA)；(c) by the sandwich type polymer composites in inert gas atmosphere
It is calcined or is calcined in inert gas atmosphere with sulphur source, selenium source or phosphorus source with volatilization property.
By the way that in the compound ferro element of sulphonated polymers microparticle surfaces, then compound poly-dopamine, intermediate folder can be formed after calcining in this way
There are double carbon-coating sandwich structures of iron compound, not only conducive to the conduction of electronics and ion, but also the diffusion of lithium ion can be shortened
Path increases the contact area of material and electrolyte, so as to greatly improve the electrochemical kinetics of material；And dopamine
Material is finally derived as carbon-coating, which is not only conducive to improve the conductivity of electrode material, but also can be existed with stabilized electrodes material
Structural stability in electrochemical process, and obtain the excellent chemical property of cyclical stability；Whole preparation process is related to
Technique be only low temperature heating water bath, centrifugation, drying, calcining etc., have simple for process, at low cost, easily-controlled experimental conditions,
The feature being easy to implement；Used chemical reagent has hypotoxicity, and serious burden will not be caused to environment.
In step (a), the sulphonated polymers microballoon is sulphonated polystyrene microballoon (SPS), and diameter is preferably
200~700nm, be made by using concentrated acid sulfonation polystyrene microsphere (existing literature Small is can refer to, 2014,10,
4975–4981)；The sulfonated polymeric fibres are sulfonated poly- divinylbenzene fiber (SPNF), diameter is preferably 20~
100nm, be made by using the poly- divinylbenzene fiber of concentrated acid sulfonation (existing literature J.Mater.Chem.A is can refer to,
2016,4,4375–4379)；It is described to contain Fe in step (a)3+Aqueous solution by into water add source of iron be formulated, institute
State mixture of the source of iron for one or more compositions in ferric nitrate, iron chloride and ferric sulfate, concentration is usually 0.01~
0.5mol/L, by changing Fe3+Concentration can regulate and control the content of iron-based compositions in the composite；It is described to add in step (a)
Hot temperature is 60~90 DEG C；It centrifuges after reaction, is washed successively with water, ethyl alcohol, is placed in baking oven dry；Step (b)
In, the concentration of trishydroxymethylaminomethane is usually 10~100mmol/L (buffered aqueous solution i.e. Tris buffer solutions), so as to ensure
Dopamine occur polymerization and generate poly-dopamine, and keep dopamine polymerization process local environment pH value substantially not
Become.By adding in trishydroxymethylaminomethane into the aqueous solution, and (dopamine is with polymerizeing for addition dopamine under agitation
The mass ratio of object microballoon or fiber is usually 1：1~10, it also can control containing for carbon in composite material by adjusting the amount of dopamine
Amount), reaction 24 hours is stirred at room temperature, can be polymerize in this way by means of dopamine on sulfonated polymer@FeOOH surfaces
Reaction generation poly-dopamine (PDA), so as to which the sulfonated polymer@FeOOH@PDA of " sandwich type " structure be made.In step (c),
The sulphur source is sulphur powder, and the selenium source is selenium powder, and phosphorus source is sodium hypophosphite；The calcination temperature for 500~700 DEG C,
Calcination time is 1~5 hour, and above-mentioned calcining carries out usually in tube furnace.During this period, sulphonated polymers and PDA derive
For carbon, and FeOOH reacts respectively with sulphur source, selenium source or phosphorus source, generates FeS respectively2, FeSe or FeP, be finally made hollow " three
The C@FeS of Mingzhi's type " structure2@C, C@FeSe@C or C@FeP@C products；If the product in step (b) is individually put in tube furnace
The C@Fe of hollow " sandwich type " structure are then made in middle calcining3O4@C。
The present invention is further described below in conjunction with embodiment.
Embodiment 1
The present embodiment provides a kind of preparation methods of hollow sandwich type iron-based negative material, it includes the following steps：
(a) sulfonated polystyrene microballoon (SPS, 0.1g, diameter about 500nm) ultrasonic disperse is contained into Fe to 200mL
(NO3)3·6H2In the aqueous solution of O (0.54g), the solution is then heated to 85 DEG C using water-bath, is reacted 30 minutes；By solution
It centrifuges, and is washed successively with water, ethyl alcohol；Obtained red solid is put into baking oven and obtains core within dry 24 hours at 60 DEG C
The SPS@FeOOH of shell structure；
(b) by product (0.1g) ultrasonic disperse in step (a) in containing Tris's (25mM, trishydroxymethylaminomethane)
In buffered aqueous solution, dopamine (DA, 0.05g) is added under stirring into the solution, continues to be stirred to react 24 hour (phase at room temperature
Between, on the surface of SPS@FeOOH polymerisation generation poly-dopamine (PDA) occurs for DA)；Reaction terminates, and centrifuges, and successively
It is washed with water, ethyl alcohol；Obtained black solid is put into baking oven and obtains " sandwich type " structure within dry 24 hours at 60 DEG C
SPS@FeOOH@PDA；
(c) product in step (b) and sulphur powder are placed in porcelain boat and are put in tube furnace that (product and sulphur powder are not necessarily required to
Mixing, as long as being placed adjacent), 500 DEG C are warming up to 1 DEG C per minute of heating rate in an inert atmosphere, and maintenance 3 is small
When.Period, SPS and PDA will be derived as carbon, and FeOOH generates FeS with sulphur powder2.Thus, finally obtain hollow " sandwich
The spherical C@FeS of type " structure2@C composites (as shown in Figure 1).
Embodiment 2
The present embodiment provides a kind of preparation method of hollow sandwich type iron-based negative material, preparation process and embodiment
It is basically identical in 1, unlike：Sulphur powder is changed to selenium powder when step (c) is calcined and hollow " sandwich type " structure is made
Spherical C@FeSe@C composites, chemical property is shown in Fig. 7.
Embodiment 3
The present embodiment provides a kind of preparation method of hollow sandwich type iron-based negative material, preparation process and embodiment
It is basically identical in 1, unlike：Spherical SPS is changed to one-dimensional SPNF nanofibers in step (a) and is made hollow " three
The fibrous C@FeS of Mingzhi's type " structure2@C composites.
Embodiment 4
The present embodiment provides a kind of preparation method of hollow sandwich type iron-based negative material, preparation process and embodiment
It is basically identical in 3, unlike：Sulphur powder is changed to selenium powder in step (c), so as to which the fibre of hollow " sandwich type " structure be made
Tie up shape C@FeSe@C composites.
Embodiment 5
The present embodiment provides a kind of preparation method of hollow sandwich type iron-based negative material, preparation process and embodiment
It is basically identical in 1, unlike：Sulphur powder is changed to sodium hypophosphite when step (c) is calcined and hollow " sandwich is made
The spherical C@FeP@C composites of type " structure.
Embodiment 6
The present embodiment provides a kind of preparation method of hollow sandwich type iron-based negative material, preparation process and embodiment
It is basically identical in 3, unlike：Sulphur powder is changed to sodium hypophosphite when step (c) is calcined, so as to which hollow " Sanming City be made
Control type " the fibrous C@FeP@C composites of structure.
Embodiment 7
The present embodiment provides a kind of preparation method of hollow sandwich type iron-based negative material, preparation process and embodiment
It is basically identical in 1, the difference is that source of iron is using FeCl in step (a)3·6H2O。
Embodiment 8
The present embodiment provides a kind of preparation method of hollow sandwich type iron-based negative material, preparation process and embodiment
It is basically identical in 1, the difference is that the product dinectly bruning obtained by step (b) is made hollow " sandwich in step (c)
The spherical C@Fe of type " structure3O4@C composites, chemical property are shown in Fig. 8.
Embodiment 9
The present embodiment provides a kind of preparation method of hollow sandwich type iron-based negative material, preparation process and embodiment
It is basically identical in 3, unlike：In step (c) by the product dinectly bruning obtained by step (b), so that hollow " Sanming City be made
Control type " the fibrous C@Fe of structure3O4@C composites.
Each iron-based material in above-described embodiment is fabricated to cathode of lithium battery, detailed process is：By cathode iron-based material,
Acetylene black, PVDF press 8:1:The ratio of 1 (mass ratio) is dispersed in a certain amount of nmp solvent, is existed with high-speed shearing machine
Half an hour is stirred under the rotating speed of 10000rpm, after slurry is sufficiently mixed uniformly, is coated with, is put into 60 DEG C of baking ovens on coating machine
It is dry；Pole piece thickness is 50~60 μm after drying, recycles roll squeezer that pole piece is depressed into the 75% of original depth, is washed into a diameter of
After the round pole piece of 13mm, dry 16h is put into 120 DEG C of vacuum drying ovens, is then placed in glove box.
In the glove box full of argon gas protection gas, using the iron-based material pole piece of above-mentioned making as working electrode, with lithium
Piece is used as to electrode, the LiPF of 1mol/L6(volume ratio 1 is dissolved in EC/EMC/DMC solvents：1：1) it is electrolyte,
Celgard2500 polypropylene screens (being purchased from Celgard companies of the U.S.) are diaphragm, are assembled into button cell；And it is filled in blue electric battery
Electro-chemical test is carried out on discharge tester (being purchased from Wuhan Land Electronic Co., Ltd.).
From SEM figures (Fig. 2 and Fig. 3) as can be seen that being answered by hollow " sandwich type " the structure iron-based obtained by template of SPS
Condensation material C@FeS2@C, C@FeSe@C and C@Fe3O4@C have uniform spherical morphology, and using SPNF as the iron obtained by template
Based composites have uniform fibrous morphology.Tiny nanometer is uniformly deposited in these microballoons or fiber
Particulate matter, illustrates uniform with the composite material pattern obtained by the method, and controllability is very good.To these microballoons or fiber
It diametrically carries out EDX element lines and sweeps analysis (see Fig. 4), should be apparent that these materials have hollow " sandwich
The structure of type ".One side carbon be distributed in microballoon or the center content of fibre diameter is minimum, illustrate in hollow knot
Structure, and the content distribution of another aspect carbon is inside and outside iron (or sulphur, selenium, oxygen) element, and in ferro element is distributed in
The centre of outer two layers of carbon illustrates in " sandwich type " structure.By carrying out X-ray diffraction analysis (Fig. 5) to these materials,
It can be seen that prepared iron base composite material is corresponding intact with the standard diagram of corresponding iron-based material, explanation is successfully prepared
Target material.The iron-based that these characterization results illustrate successfully synthesize hollow " sandwich type " structure by the preparation method is answered
Condensation material, and the preparation method favorable reproducibility have universality.
Using SPS microballoons as the C@FeS obtained by masterplate2The chemical property of@C-materials is shown in Fig. 6, and the material is 20C's
Under high magnification, reversible capacity still has 500mAh/g, and after recycling 100 times for a long time under the multiplying power of 0.1C, capacity is maintained at
1000mAh/g has been higher than the capacity of graphite-based negative material from far away.Using SPS microballoons as the C@FeSe@C materials obtained by masterplate
Chemical property (Fig. 7) display of material, reversible capacity still has 590mAh/g under the high magnification of 20C, and under the multiplying power of 0.2C
After recycling 100 times for a long time, capacity still has 1120mAh/g.Using SPS microballoons as the C@Fe obtained by masterplate3O4The electrochemistry of@C-materials
Performance is shown in Fig. 8, and reversible capacity has 500mAh/g under the high magnification of 10C, and is recycled for a long time under the multiplying power of 0.1C 100 times
Afterwards, capacity still has 1010mAh/g.The spherical C@FeS of gained in embodiment 72@C-materials are merely due to the difference of source of iron, electrical property
Can with it is basically identical in embodiment 1.Table 1 compared hollow " sandwich type " structure iron-based obtained in embodiment 1-9 and answer
Capacity data when condensation material is as lithium cell negative pole.As can be seen that two kinds of obtained FeP sills, i.e., spherical C@FeP@C and
Fibrous C@FeP@C, the capacity after reversible capacity and long-term cycle under high current is relatively low, remaining a variety of iron-based is compound
Material not only has very high capacity under high current charge-discharge multiplying power, but also capacity can be kept in long-term cyclic process
It obtains more stable.The poor performance of FeP sills should be mainly related with the embedding de- lithium electrochemical property of its material itself, and remaining
The excellent performance of material also illustrates the iron base composite material by constructing hollow " sandwich type " structure, the electrification of electrode material
Learning performance will significantly be improved.
Capacity data of the hollow sandwich type iron-based negative material of gained as lithium cell negative pole in 1 embodiment 1-9 of table
| Material | Capacity (mAh/g) under 20C | Capacity (mAh/g) after 100 cycles |
| Spherical C@FeS2@C (embodiment 1) | 500 | 1000 |
| Spherical C@FeSe@C (embodiment 2) | 590 | 1120 |
| Fibrous C@FeS2@C (embodiment 3) | 480 | 950 |
| Fibrous C@FeSe@C (embodiment 4) | 600 | 1100 |
| Spherical C@FeP@C (embodiment 5) | 350 | 700 |
| Fibrous C@FeP@C (embodiment 6) | 380 | 720 |
| Spherical C@FeS2@C (embodiment 7) | 500 | 1020 |
| Spherical C@Fe3O4@C (embodiment 8) | 500 | 1010 |
| Fibrous C@Fe3O4@C (embodiment 9) | 510 | 1020 |
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of hollow sandwich type iron-based negative material, which is characterized in that it includes the following steps：
（a）Sulphonated polymers microballoon or fiber are distributed to containing Fe3+Aqueous solution in, heating reaction, dry the first core
Shell compound；
（b）The first nucleocapsid compound is dispersed in the buffered aqueous solution containing trishydroxymethylaminomethane, in stirring bar
Dopamine is added under part and it is made to carry out polymerisation in the first nucleocapsid composite surface and obtains sandwich type polymer composites；
（c）By the sandwich type polymer composites calcined in inert gas atmosphere or with volatility
Sulphur source, selenium source or the phosphorus source of matter are calcined in inert gas atmosphere.
2. the preparation method of hollow sandwich type iron-based negative material according to claim 1, it is characterised in that：Step（a）
In, the sulphonated polymers microballoon is sulphonated polystyrene microballoon, and the sulfonated polymeric fibres are sulfonated poly- two
Ethenylbenzene fiber.
3. the preparation method of hollow sandwich type iron-based negative material according to claim 1 or claim 2, it is characterised in that：It is described
A diameter of 200 ~ 700 nm of sulphonated polymers microballoon, a diameter of 20 ~ 100nm of the sulfonated polymeric fibres.
4. the preparation method of hollow sandwich type iron-based negative material according to claim 1, it is characterised in that：Step（a）
In, it is described to contain Fe3+Aqueous solution by into water add source of iron be formulated, the source of iron be ferric nitrate, iron chloride and sulphur
The mixture of one or more compositions in sour iron.
5. the preparation method of hollow sandwich type iron-based negative material according to claim 1, it is characterised in that：Step（a）
In, the heating temperature is 60 ~ 90 DEG C；It centrifuges after reaction, is washed successively with water, ethyl alcohol, is placed in baking oven dry.
6. the preparation method of hollow sandwich type iron-based negative material according to claim 1, it is characterised in that：Step（c）
In, the sulphur source is sulphur powder, and the selenium source is selenium powder, and phosphorus source is sodium hypophosphite.
7. according to the preparation method of the hollow sandwich type iron-based negative material of claim 1 or 6, it is characterised in that：Step
（c）In, the calcination temperature is 500 ~ 700 DEG C, calcination time is 1 ~ 5 hour.
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