CN101740758A - Preparation method of vulcanized conducting polymer composite anode for lithium ion battery - Google Patents
Preparation method of vulcanized conducting polymer composite anode for lithium ion battery Download PDFInfo
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- CN101740758A CN101740758A CN201010033607A CN201010033607A CN101740758A CN 101740758 A CN101740758 A CN 101740758A CN 201010033607 A CN201010033607 A CN 201010033607A CN 201010033607 A CN201010033607 A CN 201010033607A CN 101740758 A CN101740758 A CN 101740758A
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Abstract
The invention discloses a preparation method of a vulcanized conducting polymer composite anode for a lithium ion battery. In the method, a conducting polymer of polyaniline-pyrrole is used as a main substrate, sulphur is a main active substance, the simple substance of sulphur and the conducting polymer of polyaniline-pyrrole are compounded at different temperatures by using a co-hot method, and the granularity of the powder can reach a micron size, a submicron size and a nanometer size. The anode material prepared by the method has the initial discharge capacity of 1144 mAh/g under the conditions that the constant current density is 0.2 mA/cm<2>, the charging voltage upper limit is 3.0 V, and the charging voltage lower limit is 1.5 V, and the specific capacity still maintains 929 mAh/g after 20 times of circulation. It can be seen from a CV curve that the vulcanized conducting polymer composite anode material at 250 DEG C has high capacity reversibility and favorable cyclical stability.
Description
Technical field
The present invention relates to a kind of lithium ion battery field that belongs to, be specifically related to a kind of vulcanized conducting polymer composite anode for lithium ion battery preparation methods.
Background technology
In recent decades, along with developing rapidly of battery industry, the specific energy of secondary cell is also improving constantly, 30～40Wh/kg from lead-acid battery, 40～50Wh/kg of nickel-cadmium cell, 60～80Wh/kg of Ni-MH battery develops into nineteen nineties commercial lithium ion battery and reaches 100～130Wh/kg, has now reached 200Wh/kg.Lithium secondary battery is made of positive pole, negative pole and electrolyte three parts, the battery chemistries system has determined the electrochemical reaction of battery, thereby theoretical voltage, theoretical specific capacity and the theoretical specific energy of battery have been determined, lithium ion battery is negative material with carbon, its specific capacity is higher, and the higher negative material of specific capacity develops very fast.And that the key that the limiting lithium ion cell specific capacity improves is the specific capacity of positive electrode is low excessively, and the specific capacity difficulty that increases substantially positive electrode is bigger, thereby is a very important aspect that improves the lithium secondary battery chemical property for the research of cell positive material.And accept the quantitative limitation of opinion specific volume, and it is unpractical further improving its specific capacity, exploitation has high power capacity and good reversible anodal raw material just seem particularly crucial and urgent.Studies have shown that in recent years, the sulfur-bearing positive electrode, particularly organic sulfur compound is the highest class research object of specific capacity in the positive electrode, release and storage that this class material is realized energy by the fracture and the bonding of S-S key, having high-energy-density, low price, low toxicity, active material molecular structure and advantage such as can design, is the very promising high-energy-density anode material of lithium battery of a class.
The electron conduction extreme difference of element S, when using as positive electrode, the utilance of active material S is not high, and invertibity is poor, and capacity continues to descend; And along with the carrying out of electrode reaction, Li
2The S passivation layer can generate Li with the S reaction that is dissolved in the electrolyte
2S
2Thereby, cause passivation layer to dissociate and then form the solubility polysulfide, finally the stability to electrolyte exerts an influence.At above-mentioned shortcoming, people have found three kinds of methods of improving the Li/S battery: 1) select for use specific area up to 1000m
2The absorbent charcoal material of/g is made conductive agent.Utilize its internal cavity to absorb a large amount of active materials, thereby electrode reaction is fully carried out; 2) in the process of making electrode, add lithium salts.AlexanderGorkovenko has added Li in the Li/S anode
2S
8Compound, experimental results show that material first discharge capacity reached 1000mAh/g, through still keeping the discharge capacity of 700mAh/g after 100 circulations; 3) use polymer dielectric.The phenomenon of leakage that this method occurs in the time of can effectively preventing to use liquid electrolyte and the energy density that improves integral battery door greatly reduce the possibility that Li and S directly contact simultaneously, thereby have eliminated the hidden peril of explosion of Li/S battery.
Summary of the invention
Low at lithium-sulphur cell positive electrode material poorly conductive, active material utilization, the invention provides a kind of novel can be used as lithium ion cell positive have the invertibity of discharging and recharging height, a vulcanized conducting polymer composite anode material of good cycle.
The concrete preparation method of the vulcanized conducting polymer composite anode pole piece of a kind of lithium ion battery of the present invention is as follows:
The first step: after will gathering (aniline-pyrroles) powder, sublimed sulfur and absolute ethyl alcohol adding ball mill ball milling 5～15min, obtain first mixed material;
Second step: the mixed material that the first step is obtained is packed in the glass boat of tube furnace, feeds the nitrogen deaeration to the glass boat; And the heating rate with 5 ℃/min～10 ℃/min is heated to 155 ℃ under nitrogen protection atmosphere, and under this temperature, be incubated 2h; Heating rate with 5 ℃/min～10 ℃/min is heated to 200～300 ℃ then, and behind insulation 5h under this temperature, the compound that makes sulfuration poly-(aniline-pyrroles) is a positive electrode active materials.
The 3rd step: with positive electrode active materials, conductive agent, binding agent and mass percent concentration is after 20% the normal propyl alcohol aqueous solution adds ball mill ball milling 5～15min, to obtain second mixed material;
Add the positive electrode active materials of 5g～10g, the conductive agent of 1g～5g, the binding agent of 5g～10g in the normal propyl alcohol aqueous solution of consumption: 100ml;
Conductive agent is acetylene black, carbon black, and the average grain diameter of conductive agent is 40nm.
Binding agent is poly(ethylene oxide) PEO, Kynoar PVDF, LA132 (Chengdu is organic to be produced).
The 4th step: formation thickness is 3 microns preform on the collector that second mixed material that the method that adopts scraper to be coated with obtained for the 3rd step is applied to equably;
Collector can be aluminium foil, Copper Foil, nickel foil etc., and collector can make second mixed material be uniformly distributed in wherein or the surperficial current collector material with satisfactory electrical conductivity.
Then preform under being 40 ℃～60 ℃, temperature is obtained dry sample after dry 15～24 hours;
The 5th step: the dry sample that the 4th step made is made sheet material on tablet press machine, the pole piece that cuts into 1cm * 1cm then carries out performance test;
The pressure of tablet press machine when the film-making material is 0.1MPa～0.7MPa.
The present invention is undertaken elemental sulfur and conductive polymer poly (aniline-pyrroles) compound by being total to hot method.The sulfide polymer for preparing mainly contains following advantage:
1. contain conjugated carbon chain in the molecule, can improve the conductivity of material, reduce the consumption of conductive agent, and then improve anodal specific capacity.
2. in conjunction with a sulphur atom, electrochemical equivalent is low at least for each carbon atom, the specific capacity height.
3. the dissolubility in organic electrolyte is much smaller than the micromolecule polysulfide, and cyclicity strengthens to some extent.
4. preparation is simple, the raw material cheapness, therefore is a kind of positive electrode of worth further investigation.
Description of drawings
Fig. 1 is the cycle performance figure that adopts the vulcanized conducting polymer composite anode material that the inventive method makes.
Fig. 2 is the CV curve chart that adopts the vulcanized conducting polymer composite anode material that embodiment 1 method makes.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The concrete preparation method of the vulcanized conducting polymer composite anode pole piece of a kind of lithium ion battery of the present invention is as follows:
The first step: after will gathering (aniline-pyrroles) powder, sublimed sulfur and absolute ethyl alcohol adding ball mill ball milling 5～15min, obtain first mixed material;
Second step: the mixed material that the first step is obtained is packed in the glass boat of tube furnace, feeds the nitrogen deaeration to the glass boat; And the heating rate with 5 ℃/min～10 ℃/min is heated to 155 ℃ under nitrogen protection atmosphere, and under this temperature, be incubated 2h; Heating rate with 5 ℃/min～10 ℃/min is heated to 200～300 ℃ then, and behind insulation 5h under this temperature, the compound that makes sulfuration poly-(aniline-pyrroles) is a positive electrode active materials;
The 3rd step: with positive electrode active materials, conductive agent, binding agent and mass percent concentration is after 20% the normal propyl alcohol aqueous solution adds ball mill ball milling 5～15min, to obtain second mixed material;
Add the positive electrode active materials of 5g～10g, the conductive agent of 1g～5g, the binding agent of 5g～10g in the normal propyl alcohol aqueous solution of consumption: 100ml;
Conductive agent is acetylene black, carbon black, and the average grain diameter of conductive agent is 40nm;
Binding agent is poly(ethylene oxide) PEO, Kynoar PVDF, LA132 (Chengdu is organic to be produced);
The 4th step: formation thickness is 3 microns preform on the collector that second mixed material that the method that adopts scraper to be coated with obtained for the 3rd step is applied to equably;
Collector can be aluminium foil, Copper Foil, nickel foil etc., and collector can make second mixed material be uniformly distributed in wherein or the surperficial current collector material with satisfactory electrical conductivity;
Then preform under being 40 ℃～60 ℃, temperature is obtained dry sample after dry 15～24 hours;
The 5th step: the dry sample that the 4th step made is made sheet material on tablet press machine, the pole piece that cuts into 1cm * 1cm then carries out performance test;
The pressure of tablet press machine when the film-making material is 0.1MPa～0.7MPa.
Embodiment 1:
The first step: after will gathering (aniline-pyrroles) powder, sublimed sulfur and absolute ethyl alcohol adding ball mill ball milling 10min, obtain first mixed material;
Second step: the mixed material that the first step is obtained is packed in the glass boat of tube furnace, feeds the nitrogen deaeration to the glass boat; And when under nitrogen protection atmosphere, being heated to 155 ℃ and insulation 2h with the heating rate of 10 ℃/min; When being heated to 250 ℃ with the heating rate of 10 ℃/min then and behind the insulation 5h, make sulfuration poly-(aniline-pyrroles's) compound (positive electrode active materials).
The 3rd step: with positive electrode active materials, conductive agent, binding agent and mass percent concentration is after 20% the normal propyl alcohol aqueous solution adds ball mill ball milling 10min, to obtain second mixed material;
Add the positive electrode active materials of 7.2g, the conductive agent of 3.6g, the binding agent of 6g in the normal propyl alcohol aqueous solution of consumption: 100ml;
Conductive agent is that average grain diameter is the acetylene black of 40nm.
Binding agent is LA132 (Chengdu is organic to be produced).
The 4th step: formation thickness is 3 microns preform on the collector that second mixed material that the method that adopts scraper to be coated with obtained for the 3rd step is applied to equably;
It is aluminium foil that collector is chosen.
Then preform under being 60 ℃, temperature is obtained dry sample after dry 24 hours;
The 5th step: the dry sample that the 4th step made is made sheet material on tablet press machine, the pole piece packed battery that cuts into 1cm * 1cm then carries out performance test; The pressure of tablet press machine when the film-making material is 0.5MPa.
In order to test the cycle performance that adopts the anode pole piece that the inventive method makes, adopt the blue electric battery test system of LAND BTI-10 type to carry out the constant current charge-discharge performance test:
As shown in Figure 1, at constant current density 0.2mA/cm
2Down, be limited to 3.0V on the charging voltage, be limited under the condition of 1.5V down, discharge capacity is 1144mAh/g first, and circulating, specific capacity still remains on 929mAh/g after 20 times.As seen 250 ℃ of vulcanized conducting polymer composite anode materials have very high volumetric properties and good cyclical stability as lithium ion cell positive.
The cyclic voltammetry test condition: instrument is that the IM6ex electrochemical workstation that Na (Zahner) company produces, voltage range: 1.5V～3.0V, sweep speed 0.05mV/s prick in Germany; Constant current charge-discharge loop test condition: instrument: the BTS-5V that the new Weir in Shenzhen Electronics Co., Ltd. produces.As shown in Figure 2, the CV curve of vulcanized conducting polymer composite anode material, the positive electrode oxidation peak appears at about about 2.41V, and two reduction peak at 2.04V and 2.34V place are distinguished the multistep reaction of corresponding sulphur and lithium.Wherein the peak of high potential is transformed into many lithium sulfide (Li corresponding to sulphur
2S
n, 2＜n＜8), the peak of electronegative potential then generates lithium sulfide (Li corresponding to many lithium sulfides
2S) consistent with theoretical value, 250 ℃ of vulcanized conducting polymer composite anode material capacity invertibity height as can be seen, good cycling stability.
Embodiment 2:
The first step: after will gathering (aniline-pyrroles) powder, sublimed sulfur and absolute ethyl alcohol adding ball mill ball milling 5min, obtain first mixed material;
Second step: the mixed material that the first step is obtained is packed in the glass boat of tube furnace, feeds the nitrogen deaeration to the glass boat; And insulation 2h when under nitrogen protection atmosphere, being heated to 155 ℃ with the heating rate of 5 ℃/min; Behind the insulation 5h, make sulfuration poly-(aniline-pyrroles's) compound (positive electrode active materials) when being warming up to 200 ℃ then.
The 3rd step: with positive electrode active materials, conductive agent, binding agent and mass percent concentration is after 20% the normal propyl alcohol aqueous solution adds ball mill ball milling 5min, to obtain second mixed material;
Add the positive electrode active materials of 8.4g, the conductive agent of 3g, the binding agent of 9g in the normal propyl alcohol aqueous solution of consumption: 100ml;
Conductive agent is that average grain diameter is the carbon black of 40nm.
Binding agent is poly(ethylene oxide) PEO.
The 4th step: formation thickness is 3 microns preform on the collector that second mixed material that the method that adopts scraper to be coated with obtained for the 3rd step is applied to equably;
It is Copper Foil that collector is chosen.
Then preform under being 40 ℃, temperature is obtained dry sample after dry 20 hours;
The 5th step: the dry sample that the 4th step made is made sheet material on tablet press machine, the pole piece packed battery that cuts into 1cm * 1cm then carries out performance test.
The pressure of tablet press machine when the film-making material is 0.3MPa.
As shown in Figure 1, at constant current density 0.2mA/cm
2Down, be limited to 3.0V on the charging voltage, be limited under the condition of 1.5V down, discharge capacity is 951mAh/g first, and circulating, specific capacity remains on 654mAh/g after 20 times.As seen 200 ℃ of vulcanized conducting polymer composite anode materials have higher capacity and cyclical stability preferably as lithium ion cell positive, but more a bit weaker than embodiment 1.
Embodiment 3:
The first step: after will gathering (aniline-pyrroles) powder, sublimed sulfur and absolute ethyl alcohol adding ball mill ball milling 15min, obtain first mixed material;
Second step: the mixed material that the first step is obtained is packed in the glass boat of tube furnace, feeds the nitrogen deaeration to the glass boat; And insulation 2h when under nitrogen protection atmosphere, being heated to 155 ℃ with the heating rate of 7 ℃/min; Behind the insulation 5h, make sulfuration poly-(aniline-pyrroles's) compound (positive electrode active materials) when being warming up to 300 ℃ then.
The 3rd step: with positive electrode active materials, conductive agent, binding agent and mass percent concentration is after 20% the normal propyl alcohol aqueous solution adds ball mill ball milling 10min, to obtain second mixed material;
Add the positive electrode active materials of 9.6g, the conductive agent of 1.8g, the binding agent of 3g in the normal propyl alcohol aqueous solution of consumption: 100ml;
Conductive agent is that average grain diameter is a 40nm acetylene black.
Binding agent is Kynoar PVDF.
The 4th step: formation thickness is 3 microns preform on the collector that second mixed material that the method that adopts scraper to be coated with obtained for the 3rd step is applied to equably;
It is nickel foil that collector is chosen.
Then preform under being 50 ℃, temperature is obtained dry sample after dry 15 hours;
The 5th step: the dry sample that the 4th step made is made sheet material on tablet press machine, the pole piece packed battery that cuts into 1cm * 1cm then carries out performance test.
The pressure of tablet press machine when the film-making material is 0.7MPa.
As shown in Figure 1, at constant current density 0.2mA/cm
2Down, be limited to 3.0V on the charging voltage, be limited under the condition of 1.5V down, discharge capacity is 476mAh/g first, and the specific capacity that circulates after 20 times is reduced to 287mAh/g.As seen 300 ℃ of vulcanized conducting polymer composite anode materials are relative with cyclical stability relatively poor as the lithium ion cell positive volumetric properties.
Claims (2)
1. the preparation method of a vulcanized conducting polymer composite anode for lithium ion battery is characterized in that including following preparation steps:
The first step: after will gathering (aniline-pyrroles) powder, sublimed sulfur and absolute ethyl alcohol adding ball mill ball milling 5～15min, obtain first mixed material;
Second step: the mixed material that the first step is obtained is packed in the glass boat of tube furnace, feeds the nitrogen deaeration to the glass boat; And the heating rate with 5 ℃/min～10 ℃/min is heated to 155 ℃ under nitrogen protection atmosphere, and under this temperature, be incubated 2h; Heating rate with 5 ℃/min～10 ℃/min is heated to 200～300 ℃ then, and behind insulation 5h under this temperature, the compound that makes sulfuration poly-(aniline-pyrroles) is a positive electrode active materials;
The 3rd step: with positive electrode active materials, conductive agent, binding agent and mass percent concentration is after 20% the normal propyl alcohol aqueous solution adds ball mill ball milling 5～15min, to obtain second mixed material;
Add the positive electrode active materials of 5g～10g, the conductive agent of 1g～5g, the binding agent of 5g～10g in the normal propyl alcohol aqueous solution of consumption: 100ml;
Conductive agent is acetylene black, carbon black, and the average grain diameter of conductive agent is 40nm;
Binding agent is poly(ethylene oxide) PEO, Kynoar PVDF, LA132 (Chengdu is organic to be produced);
The 4th step: formation thickness is 3 microns preform on the collector that second mixed material that the method that adopts scraper to be coated with obtained for the 3rd step is applied to equably;
Collector can be aluminium foil, Copper Foil, nickel foil etc., and collector can make second mixed material be uniformly distributed in wherein or the surperficial current collector material with satisfactory electrical conductivity;
Then preform under being 40 ℃～60 ℃, temperature is obtained dry sample after dry 15～24 hours;
The 5th step: the dry sample that the 4th step made is made sheet material on tablet press machine, the pole piece that cuts into 1cm * 1cm then carries out performance test;
The pressure of tablet press machine when the film-making material is 0.1MPa～0.7MPa.
2. the preparation method of vulcanized conducting polymer composite anode for lithium ion battery according to claim 1, it is characterized in that: the anode pole piece that makes is at constant current density 0.2mA/cm
2Down, be limited to 3.0V on the charging voltage, be limited under the condition of 1.5V down, discharge capacity is 470～1150mAh/g first, and circulating, specific capacity still remains on 280930mAh/g after 20 times.
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