CN106374097A - Preparation method of surface-controlled PANI-g-CNTs and NCM (Polyaniline-grafted-Carbon Nano Tubes and Nickel-Cobalt-Manganese) electrode material for lithium battery - Google Patents
Preparation method of surface-controlled PANI-g-CNTs and NCM (Polyaniline-grafted-Carbon Nano Tubes and Nickel-Cobalt-Manganese) electrode material for lithium battery Download PDFInfo
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Abstract
The invention relates to a preparation method of a surface-controlled PANI-g-CNTs and NCM (Polyaniline-grafted-Carbon Nano Tubes and Nickel-Cobalt-Manganese) electrode material for a lithium battery. The preparation method comprises the following steps: (1) preparing a surface-controlled PANI-g-CNTs modified material; (2) stirring a mixture in an acetone solution according to a mass ratio of 100 to (0.5 to 100) of NCM to the surface-controlled PANI-g-CNTs modified material, and carrying out ultrasonic treatment and drying; (3) carrying out reactivating treatment on the dried mixture under the condition of a nitrogen atmosphere; (4) mixing the activated mixture with PVDF (Polyvinylidene Fluoride) and KS-6 according to different ratios in an N-methyl pyrrolidone solution, baking and drying, thus obtaining the surface-controlled PANI-g-CNTs and NCM electrode material. The preparation method disclosed by the invention has the advantages of low raw material cost, environment protection, gentle preparation conditions and easiness in realizing scale production, and a lithium electrode material prepared through the preparation method has the characteristics of high rate capacity and long cycle life.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, particularly a kind of lithium battery carbon nano tube surface can
Control Polyaniline Grafted and the preparation method of nickle cobalt lithium manganate electrode material.
Background technology
It is known that becoming increasingly conspicuous the problems such as energy crisis, environmental pollution and climate warming in worldwide, lithium ion
Battery as a kind of clean reproducible energy and has height ratio capacity, high discharge voltage, light weight, steady, wide work temperature of discharging
Degree scope, long storage time, memory-less effect and the low advantage of self-discharge rate are it is expected to replace traditional fossil energy, particularly vapour
The consumer electronics quantity such as car (including pure electric automobile and hybrid vehicle etc.), mobile phone, notebook computer rapidly increase, and lead to
The market demand of lithium battery explodes.
Nickle cobalt lithium manganate (ncm, abbreviation ternary material) be a kind of lithium ion battery containing three kinds of transition metals just
Pole active substance, has specific capacity is high, charging-discharging structure is stable, structured loop life-span length, security performance are high and with low cost etc.
Feature, and it is expected to become the main positive active material of electrokinetic cell.But, due to its relatively low electrical conductivity, lead to it big
During current discharge, discharge capacity itself and cycle life can significantly reduce, and limit its multiplying power and cycle performance.Nowadays, study
The general performance improving ternary material by the method such as interpolation conductive agent, doping, cladding in lithium battery formula of personnel.
CNT (cnts) is by the one-dimensional tubular nanometer material of single or multiple lift graphite curling, by hexagonal carbon
Ring microstructure unit forms, and the polygonized structure that end section part is made up of carbocyclic ring containing pentagon, because it has unique electronic
Electric conductivity, is widely used in lithium-ion-power cell field.With conventional conductive agent compared with common conductive carbon black, graphite etc.,
CNT, as a kind of new fibrous conductive agent, can form complete three-dimensional conductive network structure；On the other hand, carbon
Nanotube has high length-diameter ratio structure it is only necessary to extremely low addition just can reach high conductivity, i.e. CNT usage amount
Fewer than other conductive carbon blacks, graphite, such that it is able to fill other more active substances, greatly improve battery capacity.Meanwhile, carbon
The addition of nanotube is also beneficial to raising battery cycle life, the high rate charge-discharge performance of especially battery is significantly carried
Rise.
At present, it is applied to conductive agent mainly granular conductive agent such as acetylene black, white carbon black etc. and threadiness in lithium battery to lead
Electric agent such as CNT, metallic fiber, vapor phase method grown carbon fiber etc..Very high Theory Conductivity is had based on CNT
The efficent electronic transmission network that (under pure nano-carbon tube room temperature, electrical conductivity is more than 5 × 105 s/cm) and high length-diameter ratio are formed, wide
General it is applied to lithium battery both positive and negative polarity conductive agent and is used alone as in lithium cell cathode material.Research finds, CNT is as electricity
Pole material exists compared with high irreversible appearance electric capacity, and CNT makes lithium ion battery early as conductive agent in electrode material component
Realize industrial scale to produce.But, due to the high-specific surface area of CNT, draw ratio and stronger Van der Waals masterpiece
With it is difficult to good be scattered in common organic solvents so as to easily reuniting or being intertwined.In order to suppress this trend,
Simultaneously facilitate effective dispersion in non-aqueous medium for the CNT, improve its dissolubility, carbon nano tube surface is carried out covalently or
Non-covalent surface modification.The surface modification of CNT introduces other stable zwitterion bases generally by its surface
Group or polymer are strengthening the repelling effect between CNT；Or introduce hydrophobic group or polymer in carbon nano tube surface
Chain, the surface energy of regulation and control CNT improving the compatibility between CNT and electrode other components, for strengthening lithium electricity
The combination property in pond, particularly high rate performance, cycle performance etc..
Content of the invention
The technical problem to be solved in the present invention is for above-mentioned the deficiencies in the prior art, provide a kind of with low cost, environmental protection,
Preparation condition is gentle, it is easy to accomplish large-scale production and the CNT table having the characteristics that high rate performance is high, having extended cycle life
The preparation method of the controlled Polyaniline Grafted in face/nickle cobalt lithium manganate electrode material.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of lithium battery carbon nano tube surface
Controlled Polyaniline Grafted and the preparation method of nickle cobalt lithium manganate electrode material, comprise the following steps:
1) the material modified preparation of the controlled Polyaniline Grafted of carbon nano tube surface: a, certain mass CNT cnts is dissolved in sulfur
In the mixed acid of acid and nitric acid；By mixture by being washed to neutrality, prepared surface carboxyl groupsization modification being dried after fully reacting
Carbon nano tube products；B, surface carboxyl groups carbon nano tube is dissolved in thionyl chloride solution, evaporative removal two after fully reacting
Chlorine sulfoxide, the carbon nano-tube modified product of prepared surface chloride；C, it is dissolved in toluene solution by carbon nano-tube modified for surface chloride
In and add certain content ethylenediamine, after fully reacting, by deionized water clean, be dried be obtained surface amination modified carbon
Nanotube intermediate product；D, carbon nano-tube modified for surface amination intermediate product and aniline are added hydrochloric acid solution by a certain percentage
In, then it is slowly added dropwise concentration for 0.05 mol/l Ammonium persulfate. reaction a period of time, finally by the mixing of filtration, water and acetone
Solution cleaning, the dry prepared material modified pani-g-cnts of the controlled Polyaniline Grafted of carbon nano tube surface；
2) the nickle cobalt lithium manganate ncm in mass ratio for 100: 0.5 ~ 100: 5 and the controlled Polyaniline Grafted of carbon nano tube surface
Material modified mixing, the mixed solution adding the mixture to acetone and alcohol is stirred, supersound process drying；
3) nickle cobalt lithium manganate crossing drying and processing and carbon nano tube surface controlled Polyaniline Grafted mixture are in nitrogen atmosphere bar
Carry out thermal activation treatment under part；
4) after thermal activation treatment terminates, it is down to room temperature and obtains head product, it is pressed 90 with Kynoar binding agent, ks-6 conductive agent
The ratio of ~ 96:1 ~ 5:0.5 ~ 5 innIn-methyl pyrrolidone solvent, mixing, baking are dried to obtain that carbon nano tube surface is controlled to be connect
Branch polyaniline and nickle cobalt lithium manganate electrode material pani-g-cnts/ncm.
In technique scheme, in step 1), the solvent mixed volume of described sulphuric acid and nitric acid is than for 3:1.
In technique scheme, in step 1), the matter of the carbon nano-tube modified intermediate product of described surface amination and aniline
Amount ratio is 1:5 ~ 10.
In technique scheme, in step 1)-a, the condition of described abundant reaction is: reacts 4 under the conditions of temperature 60 C
Hour.
In technique scheme, in step 1)-b, the condition of described abundant reaction is: in 80 DEG C of temperature, nitrogen ceiling
React 16 hours under part.
In technique scheme, in step 1)-c, the condition of described abundant reaction is: in temperature 70 C, nitrogen ceiling
React 24 hours under part.
In technique scheme, in step 3), the temperature of described thermal activation treatment is 100-400 DEG C, during thermal activation treatment
Between be 0.5-5 hour.
The invention has the beneficial effects as follows: the present invention adopts the controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electricity
Pole material is combined with nickle cobalt lithium manganate using polyaniline controlled grafting and modifying CNT and prepares.Main raw material(s) of the present invention
Using CNT, there is high conductivity, three-dimensional conductive network structure can be formed；Carbon nano tube surface of the present invention is controlled
Polyaniline Grafted and the preparation method of nickle cobalt lithium manganate electrode material, by introducing long-chain flexibility polyaniline in carbon nano tube surface
Group, improves the dispersibility of CNT (n- methyl pyrrolidone) in organic solvent, thus realizing CNT in lithium electricity
Excellent dispersibility and interface compatibility in the both positive and negative polarity component of pond；Additionally, being existed by adding the conductive agent with good dispersion
In anode formula, the charge-discharge performance of lifting battery and minimizing close the slurry time with advantages such as improve production efficiencies, have environmental protection, work
The features such as skill is simple, quick, efficient, it is had low internal resistance, long circulation life, high rate capability using being obtained further
18650 lithium ion batteries.Preparation method of the present invention has that the cost of raw material is cheap, environmental protection, and preparation condition is gentle, it is easy to accomplish rule
Modelling produce, process is simple, quick, efficient the advantages of.
Brief description
Fig. 1 is that the modification of polyaniline long-chain or unmodified carbon nano-tube power cell high rate performance figure are added in trial-production；
Fig. 2 is that the modification of polyaniline long-chain or unmodified carbon nano-tube power cell cycle performance figure are added in trial-production.
Specific embodiment
The present invention is further detailed explanation below.
Embodiment 1,
A kind of preparation method of lithium battery controlled Polyaniline Grafted of carbon nano tube surface/nickle cobalt lithium manganate electrode material, it wraps
Include following steps:
1) the material modified preparation of the controlled Polyaniline Grafted of carbon nano tube surface: a, certain mass CNT cnts is dissolved in sulfur
In the mixed acid of acid and nitric acid, the mixed volume ratio of wherein sulphuric acid and nitric acid solvent for 3:1, reacts 4 hours under the conditions of 60 DEG C；
By mixture by being washed to neutrality, prepared surface carboxyl groupsization carbon nano-tube modified product being dried；B, surface carboxyl groups carbon is received
Mitron is dissolved in thionyl chloride solution, reacts 16 hours, evaporative removal after completion of the reaction under 80 DEG C of temperature, nitrogen protective condition
Thionyl chloride, the carbon nano-tube modified product of prepared surface chloride；C, to be dissolved in toluene molten by carbon nano-tube modified for surface chloride
In liquid and add certain content ethylenediamine, react 24 hours under temperature 70 C, nitrogen protective condition, clear by deionized water
Wash, prepared surface amination carbon nano-tube modified intermediate product is dried；D, by carbon nano-tube modified for surface amination intermediate product
It is 1:5 in mass ratio with aniline, adds in hydrochloric acid solution, then be slowly added dropwise concentration to react one section for 0.05 mol/l Ammonium persulfate.
Time, change finally by the mixed solution cleaning of filtration, water and acetone, the dry controlled Polyaniline Grafted of carbon nano tube surface that is obtained
Property material pani-g-cnts；
2) pressing the nickle cobalt lithium manganate ncm mass ratio material modified with the controlled Polyaniline Grafted of carbon nano tube surface is 100: 0.5,
The mixed solution that said mixture is added acetone and alcohol is stirred, supersound process drying；
3) drying and processing being crossed nickle cobalt lithium manganate ncm and carbon nano tube surface controlled Polyaniline Grafted mixture in temperature is 300
DEG C, carry out thermal activation treatment 3 hours under the conditions of nitrogen atmosphere；
4) after thermal activation treatment terminates, it is down to room temperature and obtains head product pani-g-cnts/ncm, it is bondd with Kynoar
Agent, ks-6 conductive agent mix in n- methyl pyrrolidone solvent in 95:3:2 ratio, toast and be dried to obtain carbon nano tube surface
Controlled Polyaniline Grafted and nickle cobalt lithium manganate electrode material.Performance test is carried out to it, first discharge specific capacity is 150.5mah/
G, discharging efficiency is 142.9mah/g for 84.1%, 5c multiplying power discharging specific capacity first.
Embodiment 2,
A kind of lithium battery preparation method of the controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electrode material, it wraps
Include following steps:
1) the material modified preparation of the controlled Polyaniline Grafted of carbon nano tube surface: a, certain mass CNT cnts is dissolved in sulfur
In the mixed acid of acid and nitric acid, the mixed volume ratio of wherein sulphuric acid and nitric acid solvent for 3:1, reacts 4 hours under the conditions of 60 DEG C；
By mixture by being washed to neutrality, prepared surface carboxyl groupsization carbon nano-tube modified product being dried；B, surface carboxyl groups carbon is received
Mitron is dissolved in thionyl chloride solution, reacts 16 hours, evaporative removal after completion of the reaction under 80 DEG C of temperature, nitrogen protective condition
Thionyl chloride, the carbon nano-tube modified product of prepared surface chloride；C, to be dissolved in toluene molten by carbon nano-tube modified for surface chloride
In liquid and add certain content ethylenediamine, react 24 hours under temperature 70 C, nitrogen protective condition, clear by deionized water
Wash, prepared surface amination carbon nano-tube modified intermediate product is dried；D, by carbon nano-tube modified for surface amination intermediate product
It is 1:5 in mass ratio with aniline, adds in hydrochloric acid solution, then be slowly added dropwise concentration to react one section for 0.05 mol/l Ammonium persulfate.
Time, change finally by the mixed solution cleaning of filtration, water and acetone, the dry controlled Polyaniline Grafted of carbon nano tube surface that is obtained
Property material (pani-g-cnts)；
2) pressing the nickle cobalt lithium manganate ncm mass ratio material modified with the controlled Polyaniline Grafted of carbon nano tube surface is 100: 0.8,
The mixed solution that said mixture is added acetone and alcohol is stirred, supersound process drying；
3) drying and processing being crossed nickle cobalt lithium manganate ncm and carbon nano tube surface controlled Polyaniline Grafted mixture in temperature is 300
DEG C, carry out thermal activation treatment 3 hours under the conditions of nitrogen atmosphere；
4) after thermal activation treatment terminates, it is down to room temperature and obtains head product pani-g-cnts/ncm, it is bondd with Kynoar
Agent, ks-6 conductive agent mix in n- methyl pyrrolidone solvent in 95:3:2 ratio, toast and be dried to obtain carbon nano tube surface
Controlled Polyaniline Grafted and nickle cobalt lithium manganate electrode material.Performance test is carried out to it, first discharge specific capacity is 150.8mah/
G, discharging efficiency is 144.0mah/g for 84.7%, 5c multiplying power discharging specific capacity first.
Embodiment 3,
A kind of lithium battery preparation method of the controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electrode material, it wraps
Include following steps:
1) the material modified preparation of the controlled Polyaniline Grafted of carbon nano tube surface: a, certain mass CNT cnts is dissolved in sulfur
In the mixed acid of acid and nitric acid, the mixed volume ratio of wherein sulphuric acid and nitric acid solvent for 3:1, reacts 4 hours under the conditions of 60 DEG C；
By mixture by being washed to neutrality, prepared surface carboxyl groupsization carbon nano-tube modified product being dried；B, surface carboxyl groups carbon is received
Mitron is dissolved in thionyl chloride solution, reacts 16 hours, evaporative removal after completion of the reaction under 80 DEG C of temperature, nitrogen protective condition
Thionyl chloride, the carbon nano-tube modified product of prepared surface chloride；C, to be dissolved in toluene molten by carbon nano-tube modified for surface chloride
In liquid and add certain content ethylenediamine, react 24 hours under temperature 70 C, nitrogen protective condition, clear by deionized water
Wash, prepared surface amination carbon nano-tube modified intermediate product is dried；D, by carbon nano-tube modified for surface amination intermediate product
It is 1:10 in mass ratio with aniline, adds in hydrochloric acid solution, then be slowly added dropwise concentration for 0.05 mol/l Ammonium persulfate. reaction one
The section time, finally by the mixed solution cleaning of filtration, water and acetone, prepared carbon nano tube surface controlled Polyaniline Grafted is dried
Material modified pani-g-cnts；
2) pressing the nickle cobalt lithium manganate ncm mass ratio material modified with the controlled Polyaniline Grafted of carbon nano tube surface is 100: 0.8,
The mixed solution that said mixture is added acetone and alcohol is stirred, supersound process drying；
3) drying and processing being crossed nickle cobalt lithium manganate ncm and carbon nano tube surface controlled Polyaniline Grafted mixture in temperature is 300
DEG C, carry out thermal activation treatment 3 hours under the conditions of nitrogen atmosphere；
4) after thermal activation treatment terminates, it is down to room temperature and obtains head product pani-g-cnts/ncm, it is bondd with Kynoar
Agent, ks-6 conductive agent mix in n- methyl pyrrolidone solvent in 95:3:2 ratio, toast and be dried to obtain carbon nano tube surface
Controlled Polyaniline Grafted and nickle cobalt lithium manganate electrode material.Performance test is carried out to it, first discharge specific capacity is 152.3mah/
G, discharging efficiency is 145.8mah/g for 84.6%, 5c multiplying power discharging specific capacity first.
Embodiment 4,
A kind of lithium battery preparation method of the controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electrode material, it wraps
Include following steps:
1) the material modified preparation of the controlled Polyaniline Grafted of carbon nano tube surface: a, certain mass CNT cnts is dissolved in sulfur
In the mixed acid of acid and nitric acid, the mixed volume ratio of wherein sulphuric acid and nitric acid solvent for 3:1, reacts 4 hours under the conditions of 60 DEG C；
By mixture by being washed to neutrality, prepared surface carboxyl groupsization carbon nano-tube modified product being dried；B, surface carboxyl groups carbon is received
Mitron is dissolved in thionyl chloride solution, reacts 16 hours, evaporative removal after completion of the reaction under 80 DEG C of temperature, nitrogen protective condition
Thionyl chloride, the carbon nano-tube modified product of prepared surface chloride；C, to be dissolved in toluene molten by carbon nano-tube modified for surface chloride
In liquid and add certain content ethylenediamine, react 24 hours under temperature 70 C, nitrogen protective condition, clear by deionized water
Wash, prepared surface amination carbon nano-tube modified intermediate product is dried；D, by carbon nano-tube modified for surface amination intermediate product
It is 1:10 in mass ratio with aniline, adds in hydrochloric acid solution, then be slowly added dropwise concentration for 0.05 mol/l Ammonium persulfate. reaction one
The section time, finally by the mixed solution cleaning of filtration, water and acetone, prepared carbon nano tube surface controlled Polyaniline Grafted is dried
Material modified pani-g-cnts；
2) pressing the nickle cobalt lithium manganate ncm mass ratio material modified with the controlled Polyaniline Grafted of carbon nano tube surface is 100: 1, will
Said mixture adds the mixed solution of acetone and alcohol to be stirred, supersound process drying；
3) drying and processing being crossed nickle cobalt lithium manganate ncm and carbon nano tube surface controlled Polyaniline Grafted mixture in temperature is 300
DEG C, carry out thermal activation treatment 3 hours under the conditions of nitrogen atmosphere；
4) after thermal activation treatment terminates, it is down to room temperature and obtains head product pani-g-cnts/ncm, it is bondd with Kynoar
Agent, ks-6 conductive agent mix in n- methyl pyrrolidone solvent in 95:3:2 ratio, toast and be dried to obtain carbon nano tube surface
Controlled Polyaniline Grafted and nickle cobalt lithium manganate electrode material.Performance test is carried out to it, first discharge specific capacity is 154.4mah/
G, discharging efficiency is 148.9mah/g for 86.5%, 5c multiplying power discharging specific capacity first.
Embodiment 5,
A kind of lithium battery preparation method of the controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electrode material, it wraps
Include following steps:
1) the material modified preparation of the controlled Polyaniline Grafted of carbon nano tube surface: a, certain mass CNT cnts is dissolved in sulfur
In the mixed acid of acid and nitric acid, the mixed volume ratio of wherein sulphuric acid and nitric acid solvent for 3:1, reacts 4 hours under the conditions of 60 DEG C；
By mixture by being washed to neutrality, prepared surface carboxyl groupsization carbon nano-tube modified product being dried；B, surface carboxyl groups carbon is received
Mitron is dissolved in thionyl chloride solution, reacts 16 hours, evaporative removal after completion of the reaction under 80 DEG C of temperature, nitrogen protective condition
Thionyl chloride, the carbon nano-tube modified product of prepared surface chloride；C, to be dissolved in toluene molten by carbon nano-tube modified for surface chloride
In liquid and add certain content ethylenediamine, react 24 hours under temperature 70 C, nitrogen protective condition, clear by deionized water
Wash, prepared surface amination carbon nano-tube modified intermediate product is dried；D, by carbon nano-tube modified for surface amination intermediate product
It is 1:10 in mass ratio with aniline, adds in hydrochloric acid solution, then be slowly added dropwise concentration for 0.05 mol/l Ammonium persulfate. reaction one
The section time, finally by the mixed solution cleaning of filtration, water and acetone, prepared carbon nano tube surface controlled Polyaniline Grafted is dried
Material modified pani-g-cnts；
2) pressing the nickle cobalt lithium manganate ncm mass ratio material modified with the controlled Polyaniline Grafted of carbon nano tube surface is 100: 2, will
Said mixture adds the mixed solution of acetone and alcohol to be stirred, supersound process drying；
3) drying and processing being crossed nickle cobalt lithium manganate ncm and carbon nano tube surface controlled Polyaniline Grafted mixture in temperature is 300
DEG C, carry out thermal activation treatment 3 hours under the conditions of nitrogen atmosphere；
4) after thermal activation treatment terminates, it is down to room temperature and obtains head product pani-g-cnts/ncm, it is bondd with Kynoar
Agent, ks-6 conductive agent mix in n- methyl pyrrolidone solvent in 95:3:2 ratio, toast and be dried to obtain carbon nano tube surface
Controlled Polyaniline Grafted and nickle cobalt lithium manganate electrode material.Performance test is carried out to it, first discharge specific capacity is 152.7mah/
G, discharging efficiency is 147.2mah/g for 85.7%, 5c multiplying power discharging specific capacity first.
Embodiment 6,
A kind of lithium battery preparation method of the controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electrode material, it wraps
Include following steps:
1) the material modified preparation of the controlled Polyaniline Grafted of carbon nano tube surface: a, certain mass CNT cnts is dissolved in sulfur
In the mixed acid of acid and nitric acid, the mixed volume ratio of wherein sulphuric acid and nitric acid solvent for 3:1, reacts 4 hours under the conditions of 60 DEG C；
By mixture by being washed to neutrality, prepared surface carboxyl groupsization carbon nano-tube modified product being dried；B, surface carboxyl groups carbon is received
Mitron is dissolved in thionyl chloride solution, reacts 16 hours, evaporative removal after completion of the reaction under 80 DEG C of temperature, nitrogen protective condition
Thionyl chloride, the carbon nano-tube modified product of prepared surface chloride；C, to be dissolved in toluene molten by carbon nano-tube modified for surface chloride
In liquid and add certain content ethylenediamine, react 24 hours under temperature 70 C, nitrogen protective condition, clear by deionized water
Wash, prepared surface amination carbon nano-tube modified intermediate product is dried；D, by carbon nano-tube modified for surface amination intermediate product
It is 1:10 in mass ratio with aniline, adds in hydrochloric acid solution, then be slowly added dropwise concentration for 0.05 mol/l Ammonium persulfate. reaction one
The section time, finally by the mixed solution cleaning of filtration, water and acetone, prepared carbon nano tube surface controlled Polyaniline Grafted is dried
Material modified pani-g-cnts；
2) pressing the nickle cobalt lithium manganate ncm mass ratio material modified with the controlled Polyaniline Grafted of carbon nano tube surface is 100: 5, will
Said mixture adds the mixed solution of acetone and alcohol to be stirred, supersound process drying；
3) drying and processing being crossed nickle cobalt lithium manganate ncm and carbon nano tube surface controlled Polyaniline Grafted mixture in temperature is 300
DEG C, carry out thermal activation treatment 3 hours under the conditions of nitrogen atmosphere；
4) after thermal activation treatment terminates, it is down to room temperature and obtains head product pani-g-cnts/ncm, it is bondd with Kynoar
Agent, ks-6 conductive agent mix in n- methyl pyrrolidone solvent in 95:3:2 ratio, toast and be dried to obtain carbon nano tube surface
Controlled Polyaniline Grafted and nickle cobalt lithium manganate electrode material.Performance test is carried out to it, first discharge specific capacity is 148.8mah/
G, discharging efficiency is 83.6 % first, and 5c multiplying power discharging specific capacity is 144.6mah/g.
Above embodiment is merely illustrative and not limiting to the invention, therefore described in all scopes according to present patent application
The equivalence changes done of method or modification, be all included in the range of present patent application.
Claims (7)
1. a kind of lithium battery preparation method of the controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electrode material, its
It is characterised by, comprise the following steps:
1) the material modified preparation of the controlled Polyaniline Grafted of carbon nano tube surface: a, certain mass CNT cnts is dissolved in sulfur
In the mixed acid of acid and nitric acid；By mixture by being washed to neutrality, prepared surface carboxyl groupsization modification being dried after fully reacting
Carbon nano tube products；B, surface carboxyl groups carbon nano tube is dissolved in thionyl chloride solution, evaporative removal two after fully reacting
Chlorine sulfoxide, the carbon nano-tube modified product of prepared surface chloride；C, it is dissolved in toluene solution by carbon nano-tube modified for surface chloride
In and add certain content ethylenediamine, after fully reacting, by deionized water clean, be dried be obtained surface amination modified carbon
Nanotube intermediate product；D, carbon nano-tube modified for surface amination intermediate product and aniline are added hydrochloric acid solution by a certain percentage
In, then it is slowly added dropwise concentration for 0.05 mol/l Ammonium persulfate. reaction a period of time, finally by the mixing of filtration, water and acetone
Solution cleaning, the dry prepared material modified pani-g-cnts of the controlled Polyaniline Grafted of carbon nano tube surface；
2) the nickle cobalt lithium manganate ncm in mass ratio for 100: 0.5 ~ 100: 5 and the controlled Polyaniline Grafted of carbon nano tube surface
Material modified mixing, the mixed solution adding the mixture to acetone and alcohol is stirred, supersound process drying；
3) nickle cobalt lithium manganate crossing drying and processing and carbon nano tube surface controlled Polyaniline Grafted mixture are in nitrogen atmosphere bar
Carry out thermal activation treatment under part；
4) after thermal activation treatment terminates, it is down to room temperature and obtains head product, it is pressed 90 with Kynoar binding agent, ks-6 conductive agent
The ratio of ~ 96:1 ~ 5:0.5 ~ 5 innIn-methyl pyrrolidone solvent, mixing, baking are dried to obtain that carbon nano tube surface is controlled to be connect
Branch polyaniline and nickle cobalt lithium manganate electrode material pani-g-cnts/ncm.
2. a kind of lithium battery according to claim 1 controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electricity
The preparation method of pole material it is characterised in that: in step 1), the solvent mixed volume of described sulphuric acid and nitric acid is than for 3:1.
3. a kind of lithium battery according to claim 1 controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electricity
The preparation method of pole material it is characterised in that: in step 1), the carbon nano-tube modified intermediate product of described surface amination and aniline
Mass ratio be 1:5 ~ 10.
4. a kind of lithium battery according to claim 1 controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electricity
The preparation method of pole material it is characterised in that: in step 1)-a, the condition of described abundant reaction is: under the conditions of temperature 60 C
Reaction 4 hours.
5. a kind of lithium battery according to claim 1 controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electricity
The preparation method of pole material it is characterised in that: in step 1)-b, the condition of described abundant reaction is: protects in 80 DEG C of temperature, nitrogen
React 16 hours under the conditions of shield.
6. a kind of lithium battery according to claim 1 controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electricity
The preparation method of pole material it is characterised in that: in step 1)-c, the condition of described abundant reaction is: protects in temperature 70 C, nitrogen
React 24 hours under the conditions of shield.
7. a kind of lithium battery according to claim 1 controlled Polyaniline Grafted of carbon nano tube surface and nickle cobalt lithium manganate electricity
The preparation method of pole material it is characterised in that: in step 3), the temperature of described thermal activation treatment is 100-400 DEG C, at thermal activation
The reason time is 0.5-5 hour.
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| CN201611109891.XA CN106374097A (en) | 2016-12-02 | 2016-12-02 | Preparation method of surface-controlled PANI-g-CNTs and NCM (Polyaniline-grafted-Carbon Nano Tubes and Nickel-Cobalt-Manganese) electrode material for lithium battery |
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| CN201611109891.XA CN106374097A (en) | 2016-12-02 | 2016-12-02 | Preparation method of surface-controlled PANI-g-CNTs and NCM (Polyaniline-grafted-Carbon Nano Tubes and Nickel-Cobalt-Manganese) electrode material for lithium battery |
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| CN115911246A (en) * | 2022-12-19 | 2023-04-04 | 宁德时代新能源科技股份有限公司 | Pole piece and secondary battery comprising same |
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| CN114447302B (en) * | 2022-01-27 | 2024-02-13 | 中国科学院电工研究所 | Layered oxide/conductive agent composite material and preparation method and application thereof |
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