CN101752548A - Conductive agent dispersion liquid, electrode slurry, electrode, battery, and preparation methods thereof - Google Patents
Conductive agent dispersion liquid, electrode slurry, electrode, battery, and preparation methods thereof Download PDFInfo
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- CN101752548A CN101752548A CN200810184027A CN200810184027A CN101752548A CN 101752548 A CN101752548 A CN 101752548A CN 200810184027 A CN200810184027 A CN 200810184027A CN 200810184027 A CN200810184027 A CN 200810184027A CN 101752548 A CN101752548 A CN 101752548A
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Abstract
The invention discloses a conductive agent dispersion liquid and a preparation method thereof. The conductive agent dispersion liquid contains a conductive agent, a solvent and a dispersion agent, wherein the dispersion agent contains aromatic rings and can be bound with the surface of the conductive agent by Van der Waals force among molecules and pi-pi action force between planes; and the solubility in the first solvent at the temperature of 25 DEG C is not smaller than 10wt%. The invention also discloses an electrode slurry and a preparation method thereof, and a battery electrode prepared from the electrode slurry and a battery. As using the matter which contains the aromatic rings and can be bound with the surface of the conductive agent by Van der Waals force among molecules and pi-pi action force between planes as the dispersion agent of the conductive agent, the battery capacitance, the charging and discharging capacitance and the rate discharge property are effectively enhanced.
Description
Technical field
The present invention relates to the preparation method of a kind of conductive agent dispersion liquid and this conductive agent dispersion liquid, the invention still further relates to electrode slurry of containing above-mentioned conductive agent dispersion liquid and preparation method thereof and battery electrode that makes with this electrode slurry and the battery that comprises this battery electrode.
Background technology
Lithium ion battery since have specific energy height, operating voltage height, light weight, self discharge little, have extended cycle life, advantage such as discharge performance is stable, memory-less effect, environmental pollution are little, now be widely used on portable communications such as mobile phone, notebook computer and the electronic product.
Because lithium-nickel-cobalt-oxygen thing (LiNiCoO as anode material for lithium-ion batteries
2), lithium and cobalt oxides (LiCoO
2), lithium manganese oxide (LiMn
2O
4) and lithium iron phosphate oxide (LiFePO
4) wait the conductance of itself low, this makes the entire electrode internal resistance increase, and active material utilization is low, and polarization increases when charging and discharging currents strengthens, and battery cycle life reduces.In order to guarantee that battery electrode has the favorable charge-discharge performance, when making anode pole piece, add a certain amount of conductive agent usually, increase between active material and the collector and the conductivity between the active material particle, thereby improve the efficiency for charge-discharge of battery.For such as graphite, negative materials such as native graphite, though itself have certain conductivity, but when the battery high rate charge-discharge, because the gap that exists between the graphite granule, reduced the high rate performance of battery, therefore it is less (before adding electrode slurry to add particle usually when making pole piece in electrode slurry, its particle diameter is generally the 40-400 nanometer) conductive black, conductive agents such as acetylene black, wish the conductive black that these particles are less, conductive agents such as acetylene black can be between graphite granule, play the effect of collecting little electric current between graphite and the collector, reduce the contact resistance of electrode, the migration rate of accelerated electron, realize improving effectively the migration rate of lithium ion in electrode material, increase the conductivity of pole piece.
The method of adding conductive agents such as the less conductive black of particle, acetylene black when making pole piece in electrode slurry generally includes adhesive is dissolved in the solvent, obtain binder solution, in this binder solution, add conductive agents such as the less conductive black of active material and above-mentioned particle, acetylene black then, mix back loading to negative current collector, dry, roll-in and cut after obtain cathode pole piece.
Yet, in actual production, find to use the stability and the rheological property of the conductive agent that said method makes relatively poor, the pole piece conductivity inequality that makes simultaneously, and the internal resistance rate obviously increases, and reduced battery charging and discharging specific capacity and high rate performance.
Summary of the invention
The present inventor finds, adopting the charging and discharging capacity of the battery that above-mentioned art methods obtains and the reason that high rate performance descends is conductive agent skewness in electrode slurry, conductive agent is conductive black for example, the particle diameter of acetylene black etc. is little, particle diameter before adding conductive agent dispersion liquid only is the 40-400 nanometer usually, specific area is big, surface energy is higher, in dispersion liquid, reunite easily between the particle and form the aggregate of diameter up to 10 microns, and formed aggregate can not effectively be scatter, and in electrode slurry, it is bulky grain more than 18 microns that conductive agent forms diameter especially, it is inhomogeneous to cause conductive agent obviously to disperse in electrode slurry, the stability and the rheological property of electrode slurry have been influenced on the one hand, also make conductive agent skewness on the pole piece on the other hand, the conductivity of the battery pole piece of making thus is inhomogeneous, change in resistance is big, thereby the phenomenon of battery polarization when being carried out big multiplying power discharging, the battery that makes takes place easily, discharge capacity is low, and multiplying power discharging property is poor.
Therefore, the objective of the invention is in dispersion liquid, to disperse uneven shortcoming, provide a kind of conductive agent can evenly disperse conductive agent dispersion liquid wherein and preparation method thereof in order to overcome conductive agent of the prior art.Further, the present invention also provides electrode slurry of containing described conductive agent dispersion liquid and preparation method thereof and battery electrode of being made by above-mentioned electrode slurry and the battery that comprises this electrode.
According to conductive agent dispersion liquid of the present invention, this conductive agent dispersion liquid contains conductive agent, solvent and dispersant, wherein, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in this solvent under 25 ℃.
Another object of the present invention provides a kind of electrode slurry, this electrode slurry contains electrode active material, conductive agent, adhesive, solvent and dispersant, wherein, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in this solvent under 25 ℃.
A further object of the present invention provides a kind of battery electrode, this battery electrode comprises collector and the electrode material that loads on the collector, described electrode material is obtained except that after desolvating by electrode slurry, and wherein, described electrode slurry is above-mentioned according to electrode slurry of the present invention.
The present invention also provides a kind of battery, and this battery comprises above-mentioned battery electrode.
The present invention also provides the method for preparation according to conductive agent dispersion liquid of the present invention, this method comprises conductive agent is distributed in the dispersant solution under sonic oscillation, this dispersant solution contains the dispersant and first solvent, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in described first solvent under 25 ℃.
Preparation method according to battery electrode paste of the present invention, wherein, this method comprises mixes dispersant solution with binder solution, under sonic oscillation, be distributed to conductive agent in the gained mixed solution again, add electrode active material afterwards, described dispersant solution contains the dispersant and first solvent, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in described first solvent under 25 ℃, and described binder solution and dispersant solution are miscible.
The present inventor discovers, during the preparation conductive agent dispersion liquid, the conductive agent particle is after fragmentation under the effect of mechanical force, its broken section must adsorb dispersant does not rapidly just cause the particle after the fragmentation to reassemble, reduce conductive agent forms bigger reunion in dispersion liquid chance, and then make the conductive agent particle diameter in the dispersion liquid less, disperse more even.The present inventor further finds, for example the aromatic ring of naphthalene nucleus or phenyl ring can provide planar structure preferably, can combine with conductive agent more strongly, therefore by in preparation process, adding a kind of aromatic ring and can be of containing with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination as dispersant, conductive agent particle broken under mechanical force is preferentially combined with dispersant, avoid the conductive agent particle in dispersion liquid, to form bigger reunion, thereby improved the dispersing uniformity of conductive agent.Because conductive agent is uniformly dispersed in electrode slurries, reduced the chance that forms bigger reunion, the battery pole piece made from the electrode slurries of this conductive agent dispersion liquid has more uniform conductive rate, resistance change rate is just low more on it, reduced the generation of the polarization phenomena of battery when carrying out big multiplying power discharging, therefore the multiplying power discharging property of battery is good more, and discharge capacity is high more.For example the lithium ion battery (rated capacity is 720mAh) that makes of lithium ion battery that will obtain according to the present invention and prior art shows with the result that the current discharge of 3C carries out the multiplying power discharging property test, the discharge capacity of the lithium ion battery that the present invention obtains is all more than 540mAh, substantially exceed the 470mAh discharge capacity of the lithium ion battery that prior art obtains, had more excellent discharge capacity and a multiplying power discharging property.
Description of drawings
Fig. 1 places result after 1.5 hours for the battery electrode paste that makes according to embodiments of the invention with according to comparative example;
Fig. 2 is the viscoplasticity curve of the battery electrode paste that makes according to embodiments of the invention with according to comparative example;
Fig. 3 is the viscograph of the battery electrode paste that makes according to embodiments of the invention with according to comparative example.
Embodiment
According to conductive agent dispersion liquid provided by the invention, although as long as described conductive agent dispersion liquid contains conductive agent, solvent and dispersant, and described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, described dispersant is not less than 10 weight % in the solubility in this solvent under 25 ℃ can realize purpose of the present invention, but under the preferable case, in this conductive agent dispersion liquid, described conductive agent, the weight ratio of solvent and dispersant is 3: (15-50): (0.6-6), be preferably 3: (15-35): (2.4-3), more preferably 3: (24-28): (2.4-3).Content by making conductive agent, solvent and dispersant is in the aforementioned proportion scope, conductive agent dispersion liquid is at room temperature placed do not occurred precipitation more than 10 hours, and the particle diameter of described conductive agent in this dispersion liquid is the 2-5 micron, is preferably the 2-4 micron, more preferably the 2-3 micron.
Making described dispersant solubility in this solvent under 25 ℃ be not less than 10 weight % has dispersant enough and that be evenly distributed in order to guarantee in the dispersion liquid, thereby can fully contact with the conductive agent particle after stirring fragmentation.Under the preferable case, described dispersant is not less than 30 weight %, more preferably 30-80 weight % in the solubility in this solvent under 25 ℃.
More particularly, described dispersant can various materials with aromatic ring known in the field, as long as can be dissolved in described solvent, described aromatic ring can be carbon aromatic ring and/or hetero-aromatic ring, described carbon aromatic ring can be naphthalene nucleus, in phenyl ring and the anthracene nucleus one or more, described hetero-aromatic ring can be a pyridine ring, in pyrrole ring and the pyrimidine ring one or more, be preferably naphthalene nucleus and/or phenyl ring, more particularly, described dispersant can be the naphthols APEO, the block copolymer of phenylethylene-maleic anhydride and/or random copolymer, alkyl phenol polyoxyethylene alcohol, the sodium salt of polyvinylpyrrolidone and benzoic acid polyoxyethylene ester and DBSA and DBSA, one or more of ammonium salt etc.Described dispersant is preferably one or more in neopelex, naphthols APEO, phenylethylene-maleic anhydride resin and the polyvinylpyrrolidone, more preferably, the weight average molecular weight of described polymer is 20000-30000, is preferably 24000-28000.
Described solvent can be selected from conventional solvent, as long as can dissolve described dispersant.As being selected from pyrrolidones, acid amides, water, ether, the pure and mild ketones solvent one or more.Described alcohol can be monohydric alcohol binary or polyalcohol, and being preferably carbon number is 1-4, and more preferably carbon number is the alcohol of 2-3; It is 3-6 that described ketone is preferably carbon number, and more preferably carbon number is the ketone of 3-4, and it is 2-6 that described ether is preferably carbon number, and more preferably carbon number is the ether of 2-4.Under the preferable case, described solvent is N-methyl pyrrolidone (NMP), N, dinethylformamide, N, N-dimethylacetylamide, N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF), water, methyl alcohol, ethanol, ether and the acetone class.Experiment showed, that the above-mentioned dispersant of enumerating of the present invention all is not less than 30 weight % in the solubility in above-mentioned solvent under 25 ℃, have in addition up to 80 weight %.
Described conductive agent can be the various materials that improve electrode conductivuty, for example, can be in conductive black, acetylene black, ketjen carbon black, electrically conductive graphite, carbon nanotube, furnace black, nickel powder, copper powder, carbon fiber and the graphite one or more.Before adding the formation dispersion liquid, the particle diameter of conductive agent self is the 40-400 nanometer before also promptly contacting with solvent.
Conductive agent dispersion liquid provided by the invention can be used for the occasion that various needs provide homogeneous conductivity, for example, can be used for the preparation of battery electrode.According to different purposes, except containing mentioned component, conductive agent dispersion liquid of the present invention can also contain other various components that do not influence conductive agent dispersion liquid character, for example when described conduction dispersion liquid needing to be used for the preparation of the application of adhesive function such as battery electrode, described conduction dispersion liquid can also contain adhesive.Under the preferable case, the weight ratio of described conductive agent and described adhesive is 3: (0.5-5), be preferably 3: (1.2-2.8).
Described adhesive can be various materials with bond properties well known in the art, for example, described adhesive can be in polytetrafluoroethylene (PTFE) class, Kynoar, polyvinylidene fluoride (PVDF) class, polyvinyl chloride (PVC) class, CMC (CMC), hydroxypropyl cellulose, sodium carboxymethylcellulose, carboxymethylethylcellulose, carboxyethyl cellulose, ethyl cellulose, polymethyl methacrylate (PMMA), butadiene-styrene rubber (SBR), butadiene-styrene rubber (SBR) latex adhesive and the rubber polymer adhesive one or more.
If described adhesive is selected Kynoar (PVDF), then solvent is preferably N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, N-diethylformamide (DEF), methyl-sulfoxide (DMSO) or oxolane (THF); If described adhesive is selected polytetrafluoroethylene, butadiene-styrene rubber or their mixture and hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol or their mixture, then solvent is preferably water or ethanol.
Preparation method according to conductive agent dispersion liquid of the present invention, wherein, this method comprises conductive agent is distributed in the dispersant solution under sonic oscillation, this dispersant solution contains the dispersant and first solvent, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, described dispersant is not less than 10 weight % in the solubility in described first solvent under 25 ℃, preferably be not less than 30 weight %, more preferably 30-80 weight %.Preferably, the weight ratio of described conductive agent, first solvent and dispersant is 3: (15-35): (0.6-6), be preferably 3: (24-28): (2.4-3).In the conductive agent dispersion liquid that makes according to this method, the particle diameter of described conductive agent is the 2-4 micron, is preferably the 2-3 micron, much smaller than the particle diameter greater than 10 microns conductive agent that adopts that art methods obtains.
When conductive agent dispersion liquid provided by the invention also contains adhesive, described conductive agent the method in the dispersant solution of being distributed under sonic oscillation is preferably included mixed dispersant solution earlier with binder solution, under sonic oscillation, be distributed to conductive agent in the gained mixed solution again, described binder solution and dispersant solution are miscible, the weight ratio of conductive agent and adhesive is 3: (0.5-5), be preferably 3: (1.2-2.8).Described binder solution contains the adhesive and second solvent, described first solvent and second solvent identical or different solvent for dissolving mutually, the weight ratio of the total amount of the described conductive agent and first solvent and second solvent is 3: (15-50), be preferably 3: (20-40), more preferably 3: (24-28).
As a kind of execution mode, respectively with first solvent and second solvent obtain dispersant solution and binder solution with dispersant and adhesive described conductive agent the method in the dispersant solution of being distributed under sonic oscillation is comprised, then dispersant solution and binder solution are mixed, again conductive agent is distributed in the gained mixed solution described first solvent and the different solvent of second solvent for dissolving mutually under sonic oscillation.
As another kind of execution mode, respectively with first solvent and second solvent obtain dispersant solution and binder solution with dispersant and adhesive described conductive agent the method in the dispersant solution of being distributed under sonic oscillation is comprised, then dispersant solution and binder solution are mixed, conductive agent is distributed under sonic oscillation in the gained mixed solution, described first solvent is identical solvent with second solvent again.
As another execution mode, obtain dispersant solution with the dispersant and first solvent described conductive agent the method in the dispersant solution of being distributed under sonic oscillation is comprised, subsequently dispersant solution is mixed with adhesive, again conductive agent is distributed in the gained mixed solution under sonic oscillation.Order for described dispersant and adhesive adding does not have special requirement.
Described first solvent and second solvent can be selected from conventional solvent, as long as can dissolve described dispersant and adhesive.As can being selected from N-methyl pyrrolidone (NMP), dimethyl formamide, dimethyl formamide, N-N-dimethylacetylamide, N, a kind of in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF), water, alcohol, ether and the ketone.Described alcohol can be monohydric alcohol binary or polyalcohol, and being preferably carbon number is 1-4, and more preferably carbon number is the alcohol of 2-3; It is 3-6 that described ketone is preferably carbon number, and more preferably carbon number is the ketone of 3-4, and it is 2-6 that described ether is preferably carbon number, and more preferably carbon number is the ether of 2-4.
The method according to this invention, under sonic oscillation, be distributed in the dispersant solution that satisfies above-mentioned condition by conductive agent, the conductive agent particle is under ultrasonication on the one hand, be broken into more tiny particle in short time greatly, and based on planar structure preferably that dispersant had, conductive agent after the dispersion is preferentially combined with dispersant, and this bond strength is bigger, thereby obtains the homodisperse conductive agent dispersion liquid of conductive agent.
If dispersion frequency is low excessively, then can not farthest the fragmentation of conductive agent cluster of grains aggressiveness also be scatter equably, if but dispersion frequency is too high, then dispersed particles is meticulous, the unsaturated energy of particle surface is higher, can reunite again in the placement and flocculate, cause dispersion stability to reduce, therefore preferably, described condition of disperseing under sonic oscillation comprises that frequency of ultrasonic is 50-150kHz, 60-120kHz more preferably, the time of disperseing under sonic oscillation is 1-3 hour, more preferably 1.5-2.5 hour.
According to electrode slurry of the present invention, this electrode slurry contains electrode active material, conductive agent, adhesive, solvent and dispersant, wherein, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, described dispersant is not less than 10 weight % in the solubility in this solvent under 25 ℃, preferably be not less than 30 weight %, more preferably 30-80 weight %.Preferably, in this electrode slurry, the weight ratio of described conductive agent, adhesive, solvent and dispersant is 3: (0.5-5): (15-50): (0.6-6), be preferably 3: (1-3): (15-35): (2.4-3), more preferably 3: (1.5-2.5): (24-28): (2.5-2.8), the weight ratio of described conductive agent and electrode active material is 3: (80-120), be preferably 3: (90-110).Under preferable range, precipitation did not appear more than 10 hours according to placing under the electrode slurry room temperature of the present invention, and the conductive agent particle diameter is not less than 18 microns in the electrode slurry that obtains than existing method, the particle diameter of described conductive agent in this electrode slurry is the 5-15 micron, is preferably the 5-10 micron.
Described electrode active material can be active substance of lithium ion battery anode or lithium ion battery negative pole active materials.When described electrode active material is active substance of lithium ion battery anode, also this electrode slurry is called lithium ion battery anode glue size; When described electrode active material is lithium ion battery negative pole active materials, also this electrode slurry is called lithium ion battery cathode slurry.Described negative electrode active material has no particular limits, can embed and take off the material with carbon element of embedding repeatedly for making lithium ion, comprise in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules (MCMB), ashbury metal, silicon alloy, the mesocarbon fiber (MCF) etc. one or more or their mixture.At this moment, described adhesive can be selected from one or more in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC), the butadiene-styrene rubber (SBR).
Described positive active material can adopt the conventional all types of positive active materials that use of lithium battery in the prior art, as Li
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur).
About the preparation method of above-mentioned dispersant and conductive agent, adhesive, solvent and the dispersant among electrode slurry and the preparation method described below, can be same as described above, do not repeat them here.
Preparation method according to electrode slurry of the present invention, wherein, this method comprises mixes dispersant solution with binder solution, under sonic oscillation, disperse conductive agent in the gained mixed solution again, add electrode active material afterwards, described dispersant solution contains the dispersant and first solvent, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in described first solvent under 25 ℃, preferably be not less than 30 weight %, described binder solution and dispersant solution are miscible.Preferably, conductive agent: adhesive: (first solvent+second solvent): the weight ratio of dispersant is (80-120): 3: (0.5-5): (15-50): (0.6-6), be preferably 3: (1-3): (20-40): (2.4-3), more preferably 3: (1.5-2): (24-35): (2.4-2.8), the weight ratio of described conductive agent and electrode active material is 3: (80-120), be preferably 3: (90-110).In the electrode slurry that makes according to this method, the particle diameter of described conductive agent is the 5-15 micron, is preferably the 7-12 micron.
Preferably, described condition of disperseing under sonic oscillation comprises that frequency of ultrasonic is 50-150kHz, 60-120kHz more preferably, and the time of disperseing under sonic oscillation is 1.5-2.5 hour, more preferably 1.5-2 hour.
The battery that the present invention also provides a kind of battery electrode and made by battery electrode provided by the invention, described battery electrode comprises collector and the electrode material that loads on the collector, described electrode material is obtained except that after desolvating by electrode slurry, wherein, described electrode slurry is above-described electrode slurry.Because the electrode material that only relates to battery and electrode improves herein, there is no particular limitation to the load capacity of collector, electrode material and negative pole, barrier film and the electrolyte of battery, and their preparation method and The Nomenclature Composition and Structure of Complexes have been conventionally known to one of skill in the art.For example, described collector is conventionally known to one of skill in the art, can be selected from aluminium foil, Copper Foil, nickel plated steel strip, the Punching steel strip one or more, and positive pole of the present invention selects for use aluminium foil to make collector, and negative pole selects for use Copper Foil to make collector.
The present invention is described further below in conjunction with embodiment.
The present embodiment explanation is according to conductive agent dispersion liquid of the present invention and preparation method thereof.
With 60 the gram polyvinylpyrrolidones (available from enlightening equine skill, PVPR22K, weight average molecular weight 22100) is dissolved in 150 N that restrain, in the dinethylformamide, acetylene black (particle diameter 50 nanometers before adding) with 30 grams is distributed in the solution that obtains under sonic oscillation again, use the ultrasonic dispersing machine of the Lucky model of Shanghai sound man of virtue and ability ultrasonic instrument Co., Ltd, frequency of ultrasonic is 150kHz, jitter time is 90 minutes, records with the Hegman grind gage of the QXD model of the smart section in Tianjin Material Testing Machine that the conductive agent granular size is the 2-4 micron in the gained slurries.The gained slurries are left standstill record according to the method described above wherein after 24 hours that the conductive agent granular size is the 4-5 micron.
Comparative example 1
With the acetylene black low whipping speed with the foregoing description 1 identical source of 30 grams is the N that is distributed to 150 grams under the 1000r/min, and in the dinethylformamide, mixing time is 90 minutes.Record according to the method for the foregoing description 1 that the conductive agent granular size is the 20-35 micron in the gained slurries.The gained slurries are left standstill record according to the method described above wherein after 24 hours that the conductive agent granular size is the 38-62 micron.
The present embodiment explanation is according to electrode slurry of the present invention and electrode and preparation method thereof.
At first 15 Kynoar that restrain are dissolved in the 135 N-methyl pyrrolidones that restrain and make binder solution, subsequently with 30 the gram the naphthols APEOs (available from Britain ICI company, S-27000, weight average molecular weight is 27000) be dissolved in the N-methyl pyrrolidone of 100 grams, afterwards these two kinds of solution are mixed fully, conductive black with 30 grams is distributed in the mixed solution that obtains under sonic oscillation again, use the ultrasonic dispersing machine of the Lucky model of Shanghai sound man of virtue and ability ultrasonic instrument Co., Ltd, frequency of ultrasonic is 120kHz, jitter time is 120 minutes, records according to the method for embodiment 1 that the conductive agent granular size is the 2-3 micron in the conduction slurries.The LiCoO that in this conductive agent dispersion liquid, adds 1000 grams then
2, obtain anode sizing agent with the good luck duplicate rows star mixer mixing of planetary stirring machine Guangzhou good luck machinery plant.
It is on 0.016 millimeter the aluminium foil that above-mentioned anode sizing agent is coated on thickness, oven dry, compressing tablet and cut after, make 0.114 millimeter * 471 millimeters * 42 millimeters anode pole piece, contain the LiCoO of 5.4 grams on this anode pole piece
2
Comparative example 2
Method according to embodiment 2 is prepared electrode slurry and electrode, and different is to adopt four leaf oar formula dispersion machines of the Eumix R30 model of Fluko company that conductive agent was disperseed 120 minutes under 1000r/min.Record the conduction slurries in the conductive agent granular size be the 7-11 micron.
Comparative example 3
Method according to embodiment 2 is prepared electrode slurry and electrode, and different is not add the naphthols APEO.Record the conduction slurries in the conductive agent granular size be the 7-13 micron.
Comparative example 4
Method according to embodiment 1 is prepared electrode slurry and electrode, and different is not add the naphthols APEO, and adopt four leaf oar formula dispersion machines of the Eumix R30 model of Fluko company that conductive agent is disperseed under 1000r/min.Record the conduction slurries in the conductive agent granular size be the 11-17 micron.
The present embodiment explanation is according to electrode slurry of the present invention and electrode and preparation method thereof.
Method according to embodiment 2 is prepared, and different is that the amount of the adding of described naphthols APEO is 6 grams.Record the conduction slurries in the conductive agent granular size be the 3.5-4 micron.
Embodiment 4
The present embodiment explanation is according to electrode slurry of the present invention and electrode and preparation method thereof.
Method according to embodiment 2 is prepared, and different is that the amount of the adding of described naphthols APEO is 28 grams.Record the conduction slurries in the conductive agent granular size be the 2-3 micron.
Embodiment 5
The present embodiment explanation is according to electrode slurry of the present invention and electrode and preparation method thereof.
At first 5 polytetrafluoroethylene that restrain are dissolved in the 135 N-methyl pyrrolidones that restrain and make binder solution, neopelex with 24 grams is dissolved in the dimethyl formamide of 145 grams subsequently, again these two kinds of solution are mixed fully, acetylene black with 30 grams is distributed in the mixed solution that obtains under sonic oscillation again, use the ultrasonic dispersing machine of the Lucky model of Shanghai sound man of virtue and ability ultrasonic instrument Co., Ltd, in frequency is to disperse under the 50kHz 150 minutes, records with the Hegman grind gage of the QXD model of the smart section in Tianjin Material Testing Machine and conducts electricity that the conductive agent granular size is the 2-4 micron in the slurries.The LiCoO that in this conductive agent dispersion liquid, adds 1000 grams then
2, obtain anode sizing agent with the good luck duplicate rows star mixer mixing of Guangzhou good luck machinery plant.
It is on 0.016 millimeter the aluminium foil that above-mentioned anode sizing agent is coated on thickness, oven dry, compressing tablet and cut after, make 0.114 millimeter * 471 millimeters * 42 millimeters anode pole piece, contain the LiCoO of 5.38 grams on this anode pole piece
2
Embodiment 6
The present embodiment explanation is according to conductive agent dispersion liquid of the present invention and electrode slurry and electrode and battery and preparation method thereof.
At first 50 sodium carboxymethylcelluloses that restrain are dissolved in 300 ethanol that restrain and make binder solution, subsequently with 26 the gram the phenylethylene-maleic anhydride resins (available from SARTOMER company, weight average molecular weight is 20000) be dissolved in the N-methyl pyrrolidone of 200 grams, again these two kinds of solution are mixed fully, carbon nanotube with 30 grams is distributed in the mixed solution that obtains under sonic oscillation again, use the ultrasonic dispersing machine of the Lucky model of Shanghai sound man of virtue and ability ultrasonic instrument Co., Ltd, in frequency is to disperse under the 100kHz for 100 times, records with the Hegman grind gage of the QXD model of the smart section in Tianjin Material Testing Machine and conducts electricity that the conductive agent granular size is the 2-4 micron in the slurries.The LiCoO that in this conductive agent dispersion liquid, adds 1000 grams then
2, obtain anode sizing agent with the good luck duplicate rows star mixer mixing of Guangzhou good luck machinery plant.
It is on 0.016 millimeter the aluminium foil that above-mentioned anode sizing agent is coated on thickness, oven dry, compressing tablet and cut after, make 0.114 millimeter * 471 millimeters * 42 millimeters anode pole piece, contain the LiCoO of 5.58 grams on this anode pole piece
2
Embodiment 7
The present embodiment explanation is according to conductive agent dispersion liquid of the present invention and electrode slurry and electrode and battery and preparation method thereof.
Method according to embodiment 2 is prepared, and different is,
At first the Kynoar of 25 grams is dissolved in the N of 170 grams, make binder solution in the N-dimethylacetylamide, subsequently with 25 the gram the naphthols APEOs (available from Britain ICI company, S-27000, weight average molecular weight is 27000) mixture be dissolved in 180 the gram the N-methyl pyrrolidones in, again these two kinds of solution are mixed fully, carbon nanotube with 30 grams is distributed in the mixed solution that obtains under sonic oscillation again, use the ultrasonic dispersing machine instrument of the Lucky model of Shanghai sound man of virtue and ability ultrasonic instrument Co., Ltd manufacturer production, in frequency is to disperse under the 140kHz for 90 times, records with the Hegman grind gage of the QXD model of the smart section in Tianjin Material Testing Machine and conducts electricity that the conductive agent granular size is the 2-4 micron in the slurries.The native graphites that add 1000 grams then in this conductive agent dispersion liquid obtain cathode size with the good luck duplicate rows star mixer mixing of planetary stirring machine Guangzhou good luck machinery plant.
It is on 0.016 millimeter the Copper Foil that above-mentioned cathode size is coated on thickness, oven dry, compressing tablet and cut after, make 0.114 millimeter * 471 millimeters * 42 millimeters cathode pole piece, contain the native graphites of 3.9 grams on this cathode pole piece.
Comparative example 5
Method according to embodiment 7 is prepared, different is, do not add phenylethylene-maleic anhydride resin and naphthols polyoxyethylene ether mixture, and adopt four leaf oar formula dispersion machines of the Eumix R30 model of Fluko company that conductive agent is disperseed under 1000r/min.Record that the conductive agent granular size is the 11-17 micron in the conductive agent dispersion liquid.
Performance test
1, anode sizing agent fineness test
Adopt the Hegman grind gage Hegman grind gage of the QXD model of the smart section in Tianjin Material Testing Machine respectively the anode sizing agent that derives from embodiment 2-6 and comparative example 2-4 to be carried out the fineness test according to GB/T 1724-89, the more little expression of slurry fineness is measured the results are shown in table 1.
2, anode sizing agent rheology testing
Adopt the rotation rheology tester of Physica MCR 301 models of Anton Paar company, respectively the anode sizing agent that derives from embodiment 2-6 and comparative example 2-4 is carried out rheology testing according to the standard A STM D 7175-2005 of American Society Testing and Materials, the result of wherein measured embodiment 2-4 and the viscoplasticity of comparative example 2-4 and viscosity is respectively shown in Fig. 2 and 3.
In the viscoplasticity curve chart, the initial point of curve is low more as shown in Figure 2, and G ' and G " curve mild more, illustrate that the dispersive property of conductive agent in the electrode slurry is good more.For example, the initial point of the curve shown in the comparative example 4 among Fig. 2 is very high, and curvilinear motion is violent, and the dispersion in the anode sizing agent of comparative example 4 is greatly destroyed at this moment, and sedimentation obviously takes place, and the rheological property of slurry greatly reduces.And the initial point of the curve shown in the embodiment 4 is very low, and all keeps milder trend in a big way, and the stable dispersion that still remains of the anode sizing agent of embodiment 4 is the slurries good rheological property at this moment.
In the rheological curve as shown in Figure 3, the initial point of curve is low more, illustrate motor will expect in the dispersive property of conductive agent good more, represented curvilinear trend meets result shown in Figure 2 among Fig. 3.
Based on above-mentioned same principle the slurry rheological property of the anode sizing agent that derives from embodiment 2-6 and comparative example 2-4 is made evaluation, the result is as shown in table 1.
3, anode pole piece resistivity measurement
Adopt the four point probe internal resistance test device of the RTS-8 model of Guangzhou four point probe scientific ﹠ technical corporation respectively the anode sizing agent that derives from embodiment 2-6 and comparative example 2-4 to be carried out resistivity measurement according to electron trade standard SJ/T 10314-92, the measured table 1 that the results are shown in.
If it is inhomogeneous that conductive agent disperses in dispersant, form bigger reunion, conductive agent also can disperse inhomogeneously on the electrode plates of making thus, causes local conductive agent few or do not have conductive agent, thereby the resistivity of pole piece is increased.Therefore, resistivity is more little, and conductive agent disperses evenly more on the expression pole piece.
4, anode sizing agent stability test
The anode sizing agent that derives from embodiment 2 and comparative example 2-4 was placed 1.5-10 hour down in room temperature (25 ℃), the result of observation generation sedimentation as shown in Figure 1, wherein, Fig. 1 (a) is that embodiment 2 places the result that sedimentation took place after 1.5 hours, Fig. 1 (b) is that comparative example 2 is placed the result that sedimentation took place after 1.5 hours, obviously can find, the electrode slurry that makes according to the present invention still keeps stable dispersion after placing 1.5 hours, and the electrode slurry sedimentation that prior art obtains is obvious, and layering takes place.In addition, the present inventor also finds, along with extend to 10 hours of standing time, and almost completely sedimentation of the anode sizing agent among the comparative example 2-4, and embodiment 2-6 still keeps stable dispersion.
Table 1
| Slurry fineness/μ m | The slurry rheological property | Pole piece resistivity/ | |
| Embodiment | |||
| 2 | ??7-12 | Good | ??6-8 |
| Comparative example 2 | ??18-20 | Generally | ??15-23 |
| Comparative example 3 | ??21-23 | Bad | ??20-27 |
| Comparative example 4 | ??27-30 | Very poor | ??25-30 |
| |
??10-14 | Good | ??10-12 |
| Embodiment 4 | ??6-10 | Good | ??3-5 |
| Embodiment 5 | ??8-12 | Good | ??9-11 |
| Embodiment 6 | ??7-12 | Good | ??5-7 |
5, battery multiplying power discharging property test
Use above-mentioned positive plate, negative plate and polypropylene screen to be wound into the pole piece of square lithium ion battery according to the mode of following table 2 respectively, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent, this electrolyte is injected battery case with 3.8g/ amount only, seal, make the square lithium ion battery of LP053450ARUL.Prepare 200 identical batteries.
The lithium ion battery that obtains is carried out the multiplying power discharging property test, electric current with 1.3C charges to 4.2V (rated capacity is 720mAh) to battery E1-E1 and CS1-CS5 respectively, after shelving 20 minutes, the electric current (2160mA) that records with 3C is discharged to 3.1V, the capacity of emitting is averaged, estimate the multiplying power discharging property of battery with this, the big more explanation multiplying power discharging property of this numerical value is good more.It the results are shown in the following table 2.
Table 2
| Battery | The positive plate source | The negative plate source | Discharge capacity (mAh) | |
| ?? | Embodiment | 2 | Embodiment 7 | ??575 |
| ??CS1 | Comparative example 2 | Embodiment 7 | ??506 | |
| ??CS2 | Comparative example 2 | Comparative example 5 | ??470 | |
| ??CS3 | Comparative example 3 | Embodiment 7 | ??495 | |
| ??CS4 | Comparative example 4 | Embodiment 7 | ??485 | |
| ?? | Embodiment | 2 | Comparative example 5 | ??532 |
| ?? | Embodiment | 3 | Embodiment 7 | ??552 |
| ??E3 | Embodiment 4 | Embodiment 7 | ??568 | |
| ??E4 | Embodiment 5 | Embodiment 7 | ??560 | |
| ??E5 | Embodiment 6 | Embodiment 7 | ??569 |
From table 1 and 3 and the result of the performance test of Fig. 1-3 as can be seen, according to the size of the conductive agent particle diameter in the prepared battery slurries of method provided by the invention conductive agent particle diameter in the prepared battery slurries of existing method, and the stability that is had also is better than existing battery slurries greatly, the conductivity of the battery electrode that makes with battery slurries of the present invention is even in addition, the high-multiplying power discharge battery capacitance loss is few, has therefore improved the high rate capability of battery.And the method for prior art is owing to add dispersant, conductive agent is not carried out disperseing under sonic oscillation yet, therefore can not obtain finely dispersed electrode slurry, the particle diameter of conductive agent in electrode slurry is big, cause the battery pole piece conductivity that makes thus low, and the conductivity inequality, the battery capacity loss is serious under the high-multiplying power discharge condition.
Claims (26)
1. conductive agent dispersion liquid, this conductive agent dispersion liquid contains conductive agent, solvent and dispersant, it is characterized in that, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in this solvent under 25 ℃.
2. conductive agent dispersion liquid according to claim 1, wherein, in this conductive agent dispersion liquid, conductive agent: solvent: the weight ratio of dispersant is 3: (15-50): (0.6-6).
3. conductive agent dispersion liquid according to claim 2, wherein, in this conductive agent dispersion liquid, conductive agent: solvent: the weight ratio of dispersant is 3: (24-28): (2.4-3).
4. according to any described conductive agent dispersion liquid among the claim 1-3, wherein, described dispersant is one or more in naphthols APEO, phenylethylene-maleic anhydride resin, polyvinylpyrrolidone and the neopelex.
5. according to any described conductive agent dispersion liquid among the claim 1-3, wherein, described solvent is N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethylacetylamide, water, carbon number be the alcohol of 1-4, ketone that carbon number is 3-6 and carbon number be 2-6 ether in one or more; Described conductive agent is one or more in conductive black, acetylene black, ketjen carbon black, electrically conductive graphite, carbon nanotube, furnace black, nickel powder, copper powder and the graphite.
6. according to any described conductive agent dispersion liquid among the claim 1-3, wherein, this conductive agent dispersion liquid also contains adhesive, the weight ratio of described conductive agent and described adhesive is 3: (0.5-5), described adhesive is one or more in Kynoar, polytetrafluoroethylene, sodium carboxymethylcellulose, carboxyethyl cellulose, ethyl cellulose, carboxymethylethylcellulose, CMC, hydroxypropyl cellulose and the butadiene-styrene rubber.
7. according to any described conductive agent dispersion liquid among the claim 1-3, wherein, the particle diameter of conductive agent described in this dispersion liquid is the 2-4 micron.
8. electrode slurry, this electrode slurry contains electrode active material, conductive agent, adhesive, solvent and dispersant, it is characterized in that, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in this solvent under 25 ℃.
9. electrode slurry according to claim 8, wherein, in the described electrode slurry, conductive agent: adhesive: solvent: the weight ratio of dispersant is 3: (0.5-5): (15-50): (0.6-6), the weight ratio of described conductive agent and electrode active material is 3: (80-120).
10. according to Claim 8 or 9 described electrode slurrys, wherein, described dispersant is one or more in naphthols APEO, phenylethylene-maleic anhydride resin, alkyl phenol polyoxyethylene alcohol, polyvinylpyrrolidone, benzoic acid polyoxyethylene ester and the neopelex.
11. according to Claim 8 or 9 described electrode slurrys, wherein, described solvent is N-methyl pyrrolidone, N, dinethylformamide, N, N-dimethylacetylamide, water, carbon number be the alcohol of 1-4, ketone that carbon number is 3-6 and carbon number be 2-6 ether in one or more; Described conductive agent is one or more in conductive black, acetylene black, ketjen carbon black, electrically conductive graphite, carbon nanotube, furnace black, nickel powder, copper powder and the graphite; Described adhesive is one or more in Kynoar, polytetrafluoroethylene, sodium carboxymethylcellulose, carboxyethyl cellulose, ethyl cellulose, carboxymethylethylcellulose, CMC, hydroxypropyl cellulose and the butadiene-styrene rubber; Described electrode active material is active substance of lithium ion battery anode or lithium ion battery negative pole active materials.
12. according to Claim 8 or 9 described electrode slurrys, wherein, the particle diameter of conductive agent described in this electrode slurry is the 5-15 micron.
13. battery electrode, this battery electrode comprises collector and the electrode material that loads on the collector, described electrode material is obtained except that after desolvating by electrode slurry, it is characterized in that described electrode slurry is any described electrode slurry among the claim 8-12.
14. battery that comprises the described battery electrode of claim 13.
15. the preparation method of the described conductive agent dispersion liquid of claim 1, it is characterized in that, this method comprises conductive agent is distributed in the dispersant solution under sonic oscillation, this dispersant solution contains the dispersant and first solvent, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in described first solvent under 25 ℃.
16. preparation method according to claim 15, wherein, conductive agent: first solvent: the weight ratio of dispersant is 3: (15-35): (0.6-6).
17. according to claim 15 or 16 described preparation methods, wherein, described dispersant is one or more in naphthols APEO, phenylethylene-maleic anhydride resin, alkyl phenol polyoxyethylene alcohol, polyvinylpyrrolidone, benzoic acid polyoxyethylene ester and the neopelex.
18. according to claim 15 or 16 described preparation methods, wherein, described first solvent is that N-methyl pyrrolidone, dimethyl formamide, N-N-dimethylacetylamide, water, carbon number are that the alcohol of 1-4, ketone and the carbon number that carbon number is 3-6 are the ether of 2-6; Described conductive agent is one or more in conductive black, acetylene black, ketjen carbon black, electrically conductive graphite, carbon nanotube, furnace black, nickel powder, copper powder and the graphite.
19. preparation method according to claim 15, wherein, earlier mix dispersant solution described conductive agent the method in the dispersant solution of being distributed under sonic oscillation is comprised with binder solution, under sonic oscillation, be distributed to conductive agent in the gained mixed solution again, described binder solution and dispersant solution are miscible, the weight ratio of conductive agent and adhesive is 3: (0.5-5), described adhesive is a Kynoar, polytetrafluoroethylene, sodium carboxymethylcellulose, carboxyethyl cellulose, ethyl cellulose, carboxymethylethylcellulose, CMC, in hydroxypropyl cellulose and the butadiene-styrene rubber one or more.
20. preparation method according to claim 19, wherein, described binder solution contains the adhesive and second solvent, described first solvent or different solvents for dissolve each other identical with second solvent, and the weight ratio of the total amount of the described conductive agent and first solvent and second solvent is 3: (20-40).
21. according to claim 15 or 19 described preparation methods, wherein, the particle diameter of described conductive agent is the 2-4 micron, and described condition of disperseing under sonic oscillation comprises that frequency of ultrasonic is 50-150kHz, and the time of disperseing under sonic oscillation is 1.5-2.5 hour.
22. the preparation method of the described electrode slurry of claim 8, it is characterized in that, this method comprises mixes dispersant solution with binder solution, under sonic oscillation, be distributed to conductive agent in the gained mixed solution again, add electrode active material afterwards, described dispersant solution contains the dispersant and first solvent, described dispersant is to contain aromatic ring and can be with the material of intermolecular Van der Waals force and interplanar π-π active force and conductive agent surface combination, and described dispersant is not less than 10 weight % in the solubility in described first solvent under 25 ℃, and described binder solution and dispersant solution are miscible.
23. preparation method according to claim 22, wherein, described binder solution contains the adhesive and second solvent, described first solvent or different solvents for dissolve each other identical with second solvent, in the described electrode slurry, conductive agent: adhesive: (first solvent+second solvent): the weight ratio of dispersant is 3: (0.5-5): (15-50): (0.6-6), the weight ratio of described conductive agent and electrode active material is 3: (80-120).
24. according to claim 22 or 23 described preparation methods, wherein, described dispersant is one or more in naphthols APEO, phenylethylene-maleic anhydride resin, alkyl phenol polyoxyethylene alcohol, polyvinylpyrrolidone, benzoic acid polyoxyethylene ester and the neopelex.
25. preparation method according to claim 23, wherein, described first solvent and second solvent respectively do for oneself N-methyl pyrrolidone, dimethyl formamide, N-N-dimethylacetylamide, water, carbon number be the alcohol of 1-4, ketone that carbon number is 3-6 and carbon number be 2-6 ether in one or more; Described conductive agent is one or more in conductive black, acetylene black, ketjen carbon black, electrically conductive graphite, carbon nanotube, furnace black, nickel powder, copper powder and the graphite; Described adhesive is one or more in Kynoar, polytetrafluoroethylene, sodium carboxymethylcellulose, carboxyethyl cellulose, ethyl cellulose, carboxymethylethylcellulose, CMC, hydroxypropyl cellulose and the butadiene-styrene rubber; Described electrode active material is active substance of lithium ion battery anode or lithium ion battery negative pole active materials.
26. preparation method according to claim 22, wherein, in the described electrode slurry, the particle diameter of conductive agent is the 5-15 micron, described condition of disperseing under sonic oscillation comprises that frequency of ultrasonic is 50-150kHz, and the time of disperseing under sonic oscillation is 1.5-2.5 hour.
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| CN113036146A (en) * | 2021-03-10 | 2021-06-25 | 哈尔滨万鑫石墨谷科技有限公司 | Carbon nanotube conductive slurry and preparation method and application thereof |
| CN113036146B (en) * | 2021-03-10 | 2022-06-28 | 哈尔滨万鑫石墨谷科技有限公司 | Carbon nano tube conductive slurry and preparation method and application thereof |
| CN114141988A (en) * | 2021-11-09 | 2022-03-04 | 远景动力技术(江苏)有限公司 | Silicon-containing negative pole piece and preparation method and application thereof |
| CN114141988B (en) * | 2021-11-09 | 2023-09-08 | 远景动力技术(江苏)有限公司 | Silicon-containing negative electrode piece and preparation method and application thereof |
| CN114400303A (en) * | 2021-11-25 | 2022-04-26 | 四川英能基科技有限公司 | Positive electrode slurry for sodium ion battery, application and preparation process |
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