CN109659499A - A kind of copper silicon negative electrode of lithium ion battery preparation method - Google Patents
A kind of copper silicon negative electrode of lithium ion battery preparation method Download PDFInfo
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- CN109659499A CN109659499A CN201710938045.7A CN201710938045A CN109659499A CN 109659499 A CN109659499 A CN 109659499A CN 201710938045 A CN201710938045 A CN 201710938045A CN 109659499 A CN109659499 A CN 109659499A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The present invention is a kind of preparation method of lithium ion battery copper silicon cathode; specifically: using nano silica fume as raw material; according to 0.1 ~ 60 wt.% copper silicon mass ratio by silicon powder in-situ precipitate be cupric oxalate-silicon precursor; this forerunner's somaplasm liquid is coated on collector; by compacting, drying, protective atmosphere calcining, " Nanometer Copper-nano-silicon-collector " integrated cathode is obtained；Through subsequent cladding nano silver or conducting polymer, this copper silicon electrode can be advanced optimized.The present invention alleviates the large volume expansion and poor conductivity of nano silica fume using the excellent ductility and electric conductivity of cupric oxalate growth in situ Nanometer Copper, and electrode performance is advanced optimized by subsequent cladding nano silver and conducting polymer, the cyclical stability of final the electrode obtained is excellent.
Description
Technical field
The invention belongs to field of lithium ion battery, in particular to a kind of nano-silicon/copper composite battery electrode material and cathode
The preparation method of pole piece.
Background technique
Lithium ion battery is that modern society is wide as high-energy density, memory-less effect, environmental type rechargeable battery
General use.Currently, the new energy energy storage that popularizes of power vehicle develops so as to high-energy, high power, long-life lithium ion
The demand of battery is increasingly urgent to.
The specific capacity of traditional commerce negative electrode material graphite has been approached theoretical value (372mAhg-1), can room for promotion have
Limit；In recent years, with the Li of fast charge " zero strain " laudatory title4Ti5O12Negative electrode material is widely used in ternary material being positive
Battery system, but the lower (175mAhg of its theoretical specific capacity-1) higher cost, it is clear that these two types of negative electrode materials are unable to satisfy
Power battery the year two thousand twenty reaches the energy density demand for development of 300Wh/kg.Silicon possesses at present most as alloying lithium storage materials
High theoretical specific capacity (4200mAhg-1), slightly above graphite embedding lithium voltage platform (0.5V vs.Li+/ Li), Yi Jihuan
Protect the features such as cheap.Especially when battery is under low temperature or fast charge operating condition, silicium cathode can preferably evade conventional anode surface
The analysis lithium phenomenon of (graphite or lithium piece), so that silicium cathode becomes the important selection for promoting battery capacity and safety.
However silicon volume expansion > 300% in charge and discharge process causes cracking inside silicon electrode, electrode interior, electrode and collection
It is in electrical contact and deteriorates between fluid, capacity fails rapidly during showing as circulating battery, battery failure.Effective solution is to pass through
Silicon nanosizing is reduced to ion transmission path or silicon and other materials is compound with volume expansion effect in discharge process in buffering
It answers.Wherein, Nanostructure fabrication, such as Si nano wire (C. K. Chan; H. Peng; G. Liu; K. McIlwrath; X.
F. Zhang; R. A. Huggins;Y. Cui, Nat. Nanotech., 2008,3,31.), nc-Si film (S.
Ohara; J. Suzuki; K. Sekine; T. Takamura, A Thin Film Silicon Anode for Li-
Ion Batteries Having a Very Large Specific Capacity and Long Cycle Life. J.
Power Sources, 2004,136,303) etc. can control bulk effect makes its play Si high capacity, but preparation cost
Height, can not industrialized production.Chinese patent (CN105489839A) is using three-dimensional porous silicon-silver electrode material compared to pure three
Dimension Porous Silicon Electrode cycle performance is significantly improved: first charge-discharge coulombic efficiency has reached 88%, specific volume after 50 circulations
Amount remains close to 755mAh/g, and in circulation, 3 times special capacity fade is very fast, and circulation later shows good stable circulation
Property.But the above method generallys use silicium cathode in traditional coating process preparation, and electrode slurry contains conductive agent and binder, wherein not
Swelling occurs in EC/DMC electrolyte system for conductive polymeric binder leads to the avalanche of conductive network, aggravates the capacity of battery
Decaying.For Chinese patent (CN105489839A) by copper silicon compound, the reducing agent etc. containing C, H, O element is coated on collector,
Reduction obtains copper silicium cathode under inert atmosphere, however pyrolytic carbon is generally amorphous carbon, and conductivity and actual capacity are lower, circulation
It is not enough to maintain the stable structure of conductive network in the process.
The present invention is based on the inadaptable traditional method for manufacturing negative pole of volume expansion in silicium cathode alloying process, design soap-free emulsion polymeization
The electrode composition of agent and conductive carbon ingredients prepares the integrated electrode of metal copper silicon continuous conduction network.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of a kind of nanometer of copper silicon composite battery electrode material and cathode pole piece.
For achieving the above object, it the technical scheme is that, disperses nano silica fume in solution system, it is in situ
Precipitated nanocrystals silicon-cupric oxalate predecessor, using decomposition in situ nano-silicon/cupric oxalate under inert environments, by nano-silicon, Nanometer Copper,
The integrated electrode for having continuous conduction network is made in porous, electrically conductive collector.
A kind of copper silicon negative electrode of lithium ion battery preparation method, characterized in that the following steps are included:
1. by copper: element silicon molar ratio is (1): (0.5-8) weighs nano silica fume and mantoquita, and mantoquita is dissolved in M solvent
0.1g nano silica fume ultrasonic disperse is added afterwards, while acclimatization agent being dissolved in M solvent and obtains precipitating reagent liquid；
2. under stiring, by copper: oxalate molar ratio (1): (1-1.5) is added dropwise to precipitating reagent liquid with certain speed, in situ
Generate nano-silicon-cupric oxalate precipitating, the reaction time is 0.5-6 hour, will precipitate after reaction repeatedly washed, alcohol is washed,
Centrifugal treating；
3. operating the predecessor slurry 2. obtained to be spread evenly across on collector, by certain pressure tabletting, vacuum drying is obtained
Pole piece；
4. operating the slurry 2. obtained obtains precursor powder by vacuum drying, under the premise of not using any collector,
Predecessor powder is compressed to a pole piece；
It anneals 5. an above-mentioned pole piece is placed in calcine in inert atmosphere, obtains copper silicon integrated electrode；
6. part case study on implementation further relates to the double optimization of copper silicon integrated electrode: electrode packet to further increase electrode performance
Cover nano silver or conducting polymer.Coat the concrete operations of nano silver are as follows: the integrated electrode infiltration for 5. obtaining step 10 ~
In 60mL silver ammino solution again by reducing agent aqueous solution withn Reducing agent∶n Ag=1: 1 ratio is slowly dropped into above-mentioned solution, and reaction terminates
After pull out pole piece washing alcohol wash, be dried in vacuo.
7. the high molecular concrete operations of coated with conductive are as follows: the integrated electrode infiltration for 5. obtaining step is in 10 ~ 60mL acid
In property aniline solution, in again by aqueous oxidizing agent solution withn Oxidant∶n Ag=1: 1 ratio is pulled pole piece out after reaction and is repeatedly washed
Alcohol is washed, vacuum drying.
According to a kind of copper silicon negative electrode of lithium ion battery preparation method, it is characterized in that: mantoquita is in the 1. step
At least one of copper sulphate, copper acetate, copper nitrate, acetylacetone copper and copper chloride or several mixing；Nano silica fume purity be 99 ~
99.9999%, granularity is 30 ~ 500 nm；M solvent is at least one of water, ethyl alcohol, ethylene glycol or several mixing.
According to a kind of copper silicon negative electrode of lithium ion battery preparation method, it is characterized in that: the step 2. in precipitating reagent
For at least one of oxalic acid, sodium oxalate, potassium oxalate or several mixtures；Rate of addition is the mL/min of 0.1 mL/min ~ 10；It is heavy
Shallow lake reaction condition are as follows: reaction temperature is 20 ~ 12 DEG C, and the reaction time is 0.5 ~ 6 hour.
According to a kind of copper silicon negative electrode of lithium ion battery preparation method, it is characterized in that: the step 3. in collector
For at least one of copper foil, foam copper, copper mesh, nickel foam, titanium foam；3. and the 4. vacuum drying temperature 60 ~ 150 in step
DEG C, drying time is 0.5 ~ 18 hour；The pressure is 0.2 ~ 20MPa/cm2。
According to a kind of copper silicon negative electrode of lithium ion battery preparation method, it is characterized in that: 5. middle in situ point of the step
Solve one-time electrode reaction condition are as follows: reaction temperature be 300 ~ 800 DEG C, heating rate be 1-20 DEG C/min, the reaction time be 30 ~
400 minutes；Inert atmosphere protection atmosphere be one of high pure nitrogen, high-purity argon gas, high-purity helium or it is a kind of with hydrogen by 5 ~
99 molar ratio mixing.
According to a kind of copper silicon negative electrode of lithium ion battery preparation method, it is characterized in that: 6. middle silver-colored ammonia is molten for the step
10 ~ 28% ammonia spirits are instilled 0.1 ~ 2% silver nitrate solution for 0.1 ~ 1.5%(by liquid concentration)；Reducing agent be 0.1 ~ 2% formaldehyde or
Hydrazine hydrate aqueous solution；Coating the nano silver reaction time is 2 ~ 30 minutes, and reaction temperature is controlled at 0 ~ 25 DEG C；Coat nano Silver quality
For 5 ~ 80 wt.% of Si content.
According to a kind of copper silicon negative electrode of lithium ion battery preparation method, it is characterized in that: the step 7. in acid benzene
In amine aqueous solution, concentration of aniline is 5 ~ 50g/L, acid concentration 1mol/L；Ammonium persulfate and aniline equimolar number；Tell that acid is sulphur
It is acid, hydrochloric acid, oxalic acid, a kind of in phosphoric acid；The coated with conductive high molecular weight reactive time is 2 ~ 30 minutes, and reaction temperature is controlled 0 ~ 25
℃；Coated with conductive high molecule mass is 5 ~ 120 wt.% of Si content.
Above-mentioned copper silicon combination electrode is used as lithium ion battery negative material, and the ratio that Si accounts for composite material is 0.1 ~ 60
wt.%。
Technical effect
The invention has the following advantages that
1, silicon/cupric oxalate predecessor is designed, copper silicon integrated electrode is constructed, materials conductive is improved by three-dimensional porous conductive network
Property, padded coaming charge and discharge volume change, and coat nano silver and conducting polymer further to realize more preferably battery performance.
2, the three-dimensional conductive skeleton of integrated silicium cathode is made of peripheral porous foam metal and internal Nanometer Copper, nano-silicon
Powder is dispersed in internal porous skeleton.In electrode interior, by grass between foam copper and Nanometer Copper, Nanometer Copper and Nanometer Copper
The new pig copper interface fusion that sour copper pyrolytic obtains links one, and passes through subsequent interface alloying, compound, the conductive height of silver
The compound fusion further realized inside and outside electrode skeleton of molecule.
Detailed description of the invention
Fig. 1 is the XRD diagram of the copper silicon composite material prepared in the embodiment of the present invention one；
Fig. 2 is the scanning electron microscope low power figure of copper silicon integration cathode prepared by the embodiment of the present invention one；
Fig. 3 is the scanning electron microscope high power figure of copper silicon integration cathode prepared by the embodiment of the present invention one；
Fig. 4 is the mapping test chart of the copper silicon silver composite material of nano silver cladding prepared by the embodiment of the present invention three；
Fig. 5 is the cycle life figure under copper silicon Compound Negative button cell 200mA/g prepared by the embodiment of the present invention one；
Fig. 6 is copper silicon Compound Negative button cell first lap voltage-specific capacity curve prepared by the embodiment of the present invention three.
Specific embodiment
The present invention will be further explained with reference to the examples below, specifically carries out by implementation method below:
The present invention is a kind of preparation method of lithium ion battery copper silicon cathode, specifically: using nano silica fume as raw material, according to
Silicon powder in-situ precipitate is cupric oxalate-silicon precursor by 0.1 ~ 60 wt.% copper silicon mass ratio, this forerunner's somaplasm liquid is coated on afflux
It on body, is calcined by compacting, drying, protective atmosphere, obtains " Nanometer Copper-nano-silicon-collector " integrated cathode；Through subsequent packet
Nano silver or conducting polymer are covered, this copper silicon electrode can be advanced optimized.The present invention utilizes cupric oxalate growth in situ Nanometer Copper
Excellent ductility and electric conductivity alleviate the large volume expansion and poor conductivity of nano silica fume, and by subsequent cladding nano silver with
Conducting polymer advanced optimizes electrode performance, and the cyclical stability of final the electrode obtained is excellent, the charge and discharge at 200mA/g
The reversible capacity of electricity, material reaches 1700mAh/g.
Embodiment 1
(1) by 3.75g copper acetate dihydrate ultrasonic disperse in 300mL deionized water, 300mL second two is added in ultrasonic procedure
0.10g nano silica fume is added portionwise after obtaining clear transparent solutions in alcoholic solution, and ultrasound is placed on 60 DEG C of constant temperature with stirring for 1 hour
In water-bath.
(2) precipitating reagent is separately prepared: the water of the volume ratio 1: 1 of the 1.93g containing oxalic acid/ethylene glycol mixed solution 200mL.
(3) step (2) solution is slowly added dropwise into step (1) solution, drop speed is 2mL/min, and after dripping off, control is anti-
Answering temperature is 60 DEG C, and the reaction time is 6 hours.
(4) after reaction, product obtained in step (3) is filtered, filter cake is washed two times, until alcohol after solution clarification
It washes one time.
(5) obtained slurry is coated in the foam copper current collector cleaned up, and in 5MPa/cm2Under be pressed into thickness
Degree is placed at 120 DEG C for the pole piece of 0.25 mm and is dried in vacuo 12 hours.
(6) above-mentioned pole piece is placed in tube furnace, argon gas is passed through in tube furnace, after being kept for 3 hours at 400 DEG C
To integrated electrode.Using lithium piece as cathode in glove box, celgard2400 film is diaphragm assembled battery, and electrolyte is 1M six
Lithium fluophosphate (LiPF6)/ethylene carbonate (EC)+dimethyl carbonate (DMC).The charge and discharge at 200mA/g, the reversible appearance of material
Amount reaches 1700mAh/g.
Embodiment 2
(1) 100 mL ethylene glycol are added by 1.44g anhydrous cupric chloride ultrasonic disperse in 300mL ethylene glycol, in ultrasonic procedure,
0.10g nano silica fume is added portionwise after obtaining clear transparent solutions, ultrasonic 1h is placed in 80 DEG C of thermostat water baths with stirring.
(2) precipitating reagent is separately prepared: the ethylene glycol solution 100mL of the 1.16g containing oxalic acid.
(3) step (2) solution is slowly added dropwise into step (1) solution, drop speed is 2mL/min, and after dripping off, control is anti-
Answering temperature is 80 DEG C, and the reaction time is 5 hours.
(4) after reaction, product obtained in step (3) is filtered, filter cake is washed two times, until alcohol after solution clarification
It washes one time.
(5) obtained slurry is dried in vacuo 12 hours at 90 DEG C and obtains precursor powder, do not use any afflux
Body, by 0.015g precursor powder in 8MPa/cm2Under be pressed into diameter be 10mm a pole piece.
(6) above-mentioned pole piece is placed in tube furnace, nitrogen gas is passed through in tube furnace, kept for 4 hours at 350 DEG C
Afterwards, then at 700 DEG C it keeps obtaining integrated electrode in 2 hours.Using lithium piece as cathode in glove box, celgard2400 film be every
Film assembled battery, electrolyte are 1M lithium hexafluoro phosphate (LiPF6)/ethylene carbonate (EC)+dimethyl carbonate (DMC).
Embodiment 3
(1) 100 mL ethylene glycol are added by 1.44g anhydrous cupric chloride ultrasonic disperse in 300mL ethylene glycol, in ultrasonic procedure,
0.10g nano silica fume is added portionwise after obtaining clear transparent solutions, ultrasound is placed on 80 DEG C of thermostatical oil baths with stirring for 1 hour
In.
(2) precipitating reagent is separately prepared: the ethylene glycol solution 100mL of the 1.16g containing oxalic acid.
(3) step (2) solution is slowly added dropwise into step (1) solution, drop speed is 2mL/min, and after dripping off, control is anti-
Answering temperature is 80 DEG C, and the reaction time is 3 hours.
(4) after reaction, product obtained in step (3) is filtered, filter cake is washed two times, until alcohol after solution clarification
It washes one time.
(5) obtained slurry is coated in the foamed nickel current collector cleaned up, and in 5MPa/cm2Under be pressed into thickness
Degree is placed at 120 DEG C for the pole piece of 0.25mm and is dried in vacuo 12 hours.
(6) above-mentioned pole piece is placed in tube furnace, argon gas/hydrogen gas mixture (hydrogen content is passed through in tube furnace
5%) integrated electrode is obtained after, being kept for 5 hours at 400 DEG C.
(7) above-mentioned integrated electrode is immersed under room temperature and contains AgNO3The aqueous solution of (0.0169g) and ammonium hydroxide (0.022 μ L)
In 50mL, be added 2% formaldehyde weak solution 1.004g, reaction after ten minutes by pole piece be washed with deionized water two times, alcohol wash one time,
It is dried in vacuo 12 hours at 60 DEG C.
(8) using lithium piece as cathode in glove box, celgard2400 film is diaphragm assembled battery, and electrolyte is 1M hexafluoro
Lithium phosphate (LiPF6)/ethylene carbonate (EC)+dimethyl carbonate (DMC).
Embodiment 4
(1) 100 mL ethylene glycol are added by 1.44g anhydrous cupric chloride ultrasonic disperse in 300mL ethylene glycol, in ultrasonic procedure,
0.10g nano silica fume is added portionwise after obtaining clear transparent solutions, ultrasound is placed on 80 DEG C of thermostatical oil baths with stirring for 1 hour
In.
(2) precipitating reagent is separately prepared: the ethylene glycol solution 100mL of the 1.16g containing oxalic acid.
(3) step (2) solution is slowly added dropwise into step (1) solution, drop speed is 2mL/min, and after dripping off, control is anti-
Answering temperature is 80 DEG C, and the reaction time is 3 hours.
(4) after reaction, product obtained in step (3) is filtered, filter cake is washed two times, until alcohol after solution clarification
It washes one time.
(5) obtained slurry is coated in the foamed nickel current collector cleaned up, and in 5MPa/cm2Under be pressed into thickness
Degree is placed at 120 DEG C for the pole piece of 0.25mm and is dried in vacuo 12 hours.
(6) above-mentioned pole piece is placed in tube furnace, argon gas/hydrogen gas mixture (hydrogen content is passed through in tube furnace
5%) integrated electrode is obtained after, being kept for 5 hours at 400 DEG C.
(7) above-mentioned integrated electrode is immersed containing aniline (461.42 μ L) under room temperature and oxalic acid (1.8008g) is water-soluble
In liquid 50mL, the aqueous solution 10mL of the 0.2853g containing ammonium persulfate is added, pole piece is washed with deionized water two after ten minutes by reaction
It washes one time all over, alcohol, is dried in vacuo 12 hours at 60 DEG C.
(8) using lithium piece as cathode in glove box, celgard2400 film is diaphragm assembled battery, and electrolyte is 1M hexafluoro
Lithium phosphate (LiPF6)/ethylene carbonate (EC)+dimethyl carbonate (DMC).
Claims (10)
1. a kind of copper silicon negative electrode of lithium ion battery, characterized in that the following steps are included:
1. by copper: element silicon molar ratio is (1): (0.5-8) weighs nano silica fume and mantoquita, and mantoquita is dissolved in M solvent
0.1g nano silica fume ultrasonic disperse is added afterwards, while acclimatization agent being dissolved in M solvent and obtains precipitating reagent liquid；
2. under stiring, by copper: oxalate molar ratio (1): (1-1.5) is added dropwise to precipitating reagent liquid with certain speed, reaction
Time is 0.5-6 hours, after reaction by precipitating is repeatedly washed, alcohol is washed, centrifugal treating；
3. operating the slurry 2. obtained, by being coated on compaction drying on collector, a pole piece is obtained；
4. operating the slurry 2. obtained obtains precursor powder by vacuum drying, direct pressing obtains a pole piece；
5. a pole piece is placed in calcine by steps in protective atmosphere, copper silicon integrated electrode can be obtained；
6. to further increase electrode performance, electrode-clad nano silver: will 5. in electrode slice be placed in silver ammino solution and infiltrate, be added dropwise
Reducing agent reduction can obtain the copper silicon composite integrated polarizing electrode of nano silver cladding；
7. electrode-clad conducting polymer: will 5. middle electrode slice be placed in acid aniline solution to further increase electrode performance
Infiltration, oxidant reduction, which is added dropwise, can obtain the copper silicon composite integrated polarizing electrode of conducting polymer cladding.
2. a kind of copper silicon negative electrode of lithium ion battery according to claim 1, it is characterized in that: the step 1. in, it is described
Solvent is at least one of water, ethyl alcohol, ethylene glycol or several mixing；The ultrasonic disperse time is 1~120min.
3. a kind of copper silicon negative electrode of lithium ion battery according to claim 1, it is characterized in that: mantoquita is in the 1. step
At least one of copper sulphate, copper acetate, copper nitrate, acetylacetone copper and copper chloride or several mixing；Nano silica fume purity is 99
~99.9999%, granularity is 30~500nm；M solvent is at least one of water, ethyl alcohol, ethylene glycol or several mixing.
4. a kind of copper silicon lithium ion battery cathode according to claim 1, it is characterized in that: speed is added dropwise in the 2. step
Degree is 0.1mL/min~10mL/min；Precipitation reaction condition are as follows: reaction temperature is 20~80 DEG C, and the reaction time is 0.5~6 small
When.
5. a kind of copper silicon lithium ion battery cathode according to claim 1, it is characterized in that: 3. described collect described in step
Fluid is at least one of copper foil, foam copper, copper mesh, nickel foam, titanium foam；The pressure is 0.2~20MPa/cm2。
6. a kind of copper silicon lithium ion battery cathode told according to claim 1, it is characterized in that: described 3. and 4. true in step
60~150 DEG C of empty drying temperature, drying time are 0.5~18 hour.
7. the pressure is 0.2~20MPa/cm2。
8. a kind of copper silicon lithium ion battery cathode according to claim 1, it is characterized in that: 5. described forge described in step
Burning reaction temperature is 300~800 DEG C, and the reaction time is 30~400 minutes, and heating rate is 1~20 DEG C/min；Inert atmosphere is protected
Shield atmosphere is one of high pure nitrogen, high-purity argon gas, high-purity helium or a kind of mixes with hydrogen by 5~99 molar ratio.
9. a kind of copper silicon lithium ion battery cathode according to claim 1, it is characterized in that: silver-colored ammonia is molten in the 6. step
Liquid is 10~60mL, and concentration is 0.1~1.5%；The formaldehyde or hydrazine hydrate solution that the reducing agent is 0.1~2%, reducing agent ratio
Forn Reducing agent∶n Ag=1:1；The reaction time is 2~30 minutes, and reaction temperature is 0~25 DEG C.
10. a kind of copper silicon lithium ion battery cathode according to claim 1, it is characterized in that: aniline in the 7. step
Solution is 10~60mL, and concentration is 5~50g/L；Tell acid for a kind of, concentration 1mol/L in sulfuric acid, hydrochloric acid, oxalic acid, phosphoric acid；
The oxidant ammonium persulfate, ratio aren Oxidant∶n Aniline=1:1；The reaction time is 2~30 minutes, and reaction temperature is 0~25
℃。
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| NING LIN 等: "Synchronous synthesis of a Si/Cu/C ternary nanocomposite as an anode for Li ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 黄燕华 等: "多孔硅／铜复合负极材料的制备及其电化学性能", 《厦门大学学报（自然科学版）》 * |
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| CN109659499B (en) | 2021-12-10 |
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