CN109841834B - Composite conductive agent, preparation method thereof and application of composite conductive agent in positive electrode slurry - Google Patents
Composite conductive agent, preparation method thereof and application of composite conductive agent in positive electrode slurry Download PDFInfo
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Abstract
The invention discloses a composite conductive agent, a preparation method thereof and application thereof in positive electrode slurry. The composite conductive agent is composite conductive slurry, a solvent in the composite conductive slurry is an organic solvent, and conductive particles comprise acetylene black, conductive graphite, carbon nanofibers, carbon nanotubes and graphene; moreover, the mass ratio of the acetylene black to the conductive carbon black is 1 (0.2-5), and the mass ratio of the carbon nanofibers, the carbon nanotubes and the graphene is 1 (0.2-5) to 0.2-5. The composite conductive agent disclosed by the invention has a good point-line-surface all-directional conductive network, and conductive particles in the composite conductive agent and active substances form larger contact points, so that the conductive performance of an electrode plate can be greatly improved, the polarization of the electrode plate is reduced, the internal resistance of a battery is reduced, and the performance of the battery is improved.
Description
Technical Field
The invention relates to the technical field of preparation of conductive agents for anode materials, relates to a composite conductive agent, a preparation method and application thereof, and particularly relates to a composite conductive agent, a preparation method and application thereof in anode slurry.
Background
The ternary positive electrode material is mainly applied to automobile power batteries. As the anode material of the lithium ion battery, the electrode material must be ensured to be a good mixed conductor of ions and electrons, and a certain amount of conductive substances are added to play a role in collecting micro-current between active substances and between the active substances and a current collector, so that the contact resistance of the electrode is reduced, the moving rate of electrons is accelerated, and meanwhile, the migration rate of lithium ions in the electrode material can be effectively improved, thereby improving the charging and discharging efficiency of the electrode.
At present, the conductive agents added into the anode material mainly comprise acetylene black, carbon nanofibers, graphite conductive agents, graphene and the like. However, these conventional conductive agents have problems that they cannot form a conductive mesh or produce a good contact point with an active material when used alone, are poor in conductivity, high in resistance, and are easy to polarize electrodes. In addition, the conventional conductive agent can form lipid substances on the surface due to the manufacturing process and long-time storage in the air, so that the conductivity is influenced, the conventional conductive agent is not easy to uniformly disperse in the anode slurry, and the two problems restrict the application of the conductive agent in the preparation of pole pieces and batteries.
CN 105958074 a discloses a graphene composite conductive agent, which comprises the following components in parts by mass: 80-120 parts of graphene, 20-45 parts of acetylene black, 30-45 parts of nonylphenol polyoxyethylene ether, 10-25 parts of monoethanolamine, 200-300 parts of solvent, 2-3 parts of assistant, 7-10 parts of conductive high molecular agent, 2-4 parts of glass beads and 3-8 parts of acetylacetone iridium. The obtained conductive agent has strong electron conductivity and uniform heat conduction, has strong liquid absorption and retention capacity when being doped into a lithium ion battery, and improves the 2C multiplying power of the lithium ion battery by 6-10%. However, the conductive paste only forms point-like conduction, but does not form a conductive network of a point-line surface, has poor conductivity, high internal resistance and easy electrode polarization, and the conductive agent which is not subjected to activation and surface cleaning is placed in the air for a long time after being prepared into conductive paste, so that a lipid substance is formed on the surface, and the conductivity of the conductive paste can be influenced to a certain degree.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a composite conductive agent and a method for preparing the same. The composite conductive agent disclosed by the invention has a good point-line-surface all-directional conductive network, and conductive particles in the composite conductive agent and active substances form larger contact points, so that the conductive performance of an electrode plate can be greatly improved, the polarization of the electrode plate is reduced, the internal resistance of a battery is reduced, and the performance of the battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a composite conductive agent, wherein the composite conductive agent is a composite conductive paste, a solvent in the composite conductive paste is an organic solvent, and conductive particles include acetylene black, conductive graphite, carbon nanofibers (VGCF), carbon nanotubes, and graphene;
the mass ratio of the acetylene black to the conductive carbon black is 1 (0.2-5), and the mass ratio of the carbon nanofibers, the carbon nanotubes and the graphene is 1 (0.2-5) to 0.2-5.
In the composite conductive agent of the present invention, the mass ratio of the acetylene black to the conductive carbon black is 1 (0.2 to 5), for example, 1:0.2, 1:0.5, 1:0.7, 1:1, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:3.3, 1:3.5, 1:4, 1:4.5, or 1:5, preferably 1:1.
In the composite conductive agent, the mass ratio of the carbon nanofibers, the carbon nanotubes and the graphene is 1 (0.2-5) to 0.2-5, for example, 1:0.2:1, 1:0.5:2, 1:1:1, 1:1:0.5, 1:1:2, 1:1:3, 1:1:5, 1:2:0.5, 1:2:1, 1:2:2, 1:2:4, 1:2:5, 1:3:1, 1:3:2, 1:3:3, 1:3:5, 1:4:1, 1:4:2 or 1:4: 5.
The composite conductive agent disclosed by the invention not only contains rigid conductive particle acetylene black and conductive graphite, but also contains flexible carbon nanofibers, carbon nanotubes and graphene. Wherein, the conductivity of the rigid conductive particles is mainly point-to-point contact; the carbon nano tube belongs to flexible nano particles, and the conductivity is mainly line-to-point contact; graphene belongs to flexible thin-sheet nanoparticles, and the conductivity aspect is mainly surface-to-point contact. The five conductive particles with proper content are used to form the composite conductive agent with excellent performance, and within the content proportion range of the invention, a good point-line-surface omnibearing conductive network can be formed, and more contact points can be formed between the conductive particles in the composite conductive agent and active substances, so that the conductive performance of an electrode plate can be greatly improved, the polarization of the electrode plate can be reduced, the internal resistance of a battery can be reduced, and the performance of the battery can be improved.
The 'nano particles' involved in the invention comprise both granular (such as acetylene black) and linear (such as nano carbon fibers and carbon nano tubes) and lamellar (such as graphene), and the composite conductive agent has an excellent network structure and has the property of having very good contact points with an active material, and the proper content of the rigid and flexible conductive particles with the characteristic features can not be matched.
Preferably, the organic solvent is N-Methyl pyrrolidone (NMP).
As a preferable technical scheme of the composite conductive agent, conductive particles of the composite conductive paste are composed of acetylene black, conductive graphite, carbon nanofibers, carbon nanotubes and graphene, and in this case, the effect of improving the conductive performance by matching the conductive particles is more remarkable.
More preferably, the composite conductive paste is composed of a first composite conductive paste and a second composite conductive paste, the first conductive paste is a paste obtained by dispersing acetylene black and conductive carbon black in an organic solvent and optionally polyvinylpyrrolidone (PVP) according to a mass ratio of 1 (0.2-5), and the second composite conductive paste is a paste obtained by dispersing carbon nanofibers, carbon nanotubes and graphene in an organic solvent and optionally PVP according to a mass ratio of 1 (0.2-5) to (0.2-5). According to the preferred technical scheme, acetylene black and conductive carbon black are dispersed according to a specific mass ratio to prepare first composite conductive slurry, then flexible carbon nanofibers, carbon nanotubes and graphene are dispersed according to a specific mass ratio to prepare second composite conductive slurry, and finally the two types of slurry are mixed to obtain the composite conductive slurry, so that the rigid conductive particles and the flexible conductive particles can be matched to form a better conductive network and more contact points with active substances, and the best effect of improving conductivity is achieved.
In this preferred embodiment, the optional PVP means: PVP may or may not be added. Preferably, PVP is added.
Preferably, the solid content of the first composite conductive paste is 10% to 30%, such as 10%, 12%, 15%, 17%, 20%, 22%, 23%, 24%, 26%, 28%, or 30%, etc.
Preferably, the solid content of the second composite conductive paste is 7% to 9%, such as 7%, 7.5%, 8%, 8.2%, 8.5%, or 9%, etc., preferably 8%.
Preferably, the mass ratio of the first composite conductive paste to the second composite conductive paste is (1-3): 1, such as 1:1, 1.2:1, 1.5:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 2.8:1 or 3:1, and the like, preferably 2: 1.
As a preferred technical scheme of the composite conductive agent, the acetylene black is acetylene black modified by nano aluminum powder.
Preferably, the mass percentage of the nano aluminum powder is 5% based on 100% of the total mass of the acetylene black modified by the nano aluminum powder.
Preferably, the acetylene black is acetylene black with an acetone surface activated, and through the acetone surface activation, on one hand, impurities on the surface of the acetylene black can be removed, and on the other hand, the activity of the acetylene black can be increased, so that the subsequent synergistic promotion effect with other conductive fillers can be facilitated.
Preferably, the conductive graphite is acetone surface activated conductive graphite, and through the surface activation of acetone, on one hand, impurities on the surface of the conductive graphite can be removed, and on the other hand, the activity of the conductive graphite can be increased, so that the subsequent synergistic promotion effect with other conductive fillers is facilitated.
Preferably, the diameter of the filamentous nanocarbon is 100nm to 200nm, such as 100nm, 120nm, 130nm, 140nm, 150nm, 165nm, 180nm, 200nm, or the like; the length-diameter ratio is 100 nm-500 nm.
Preferably, the carbon nanotubes are single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
The term "single-walled carbon nanotube and/or multi-walled carbon nanotube" as used herein means that the carbon nanotube may be a single-walled carbon nanotube, a multi-walled carbon nanotube, or a mixture of a single-walled carbon nanotube and a multi-walled carbon nanotube.
In the present invention, a "Single-walled Carbon Nanotube" is a Single-walled Carbon Nanotube (SWCNTs); the "Multi-walled Carbon Nanotube" is a Multi-walled Carbon Nanotube (MWCNTs).
More preferably, the carbon nanotubes are multi-layered carbon nanotubes. According to the invention, the multilayer carbon nanotubes, other flexible conductive particle carbon nanofibers and graphene are preferably matched for use, so that a better conductive network is formed, and the conductive performance is improved.
In a second aspect, the present invention provides a method for producing the composite conductive agent according to the first aspect, the method comprising the steps of:
and dispersing conductive particles containing acetylene black, conductive graphite, carbon nanofibers, carbon nanotubes and graphene into PVP (polyvinyl pyrrolidone) which can be selected as an organic solvent to obtain composite conductive slurry, namely the composite conductive agent.
In this method, "optional PVP" means: PVP may or may not be added. Preferably, PVP is added.
Preferably, the organic solvent is NMP.
As a preferred technical scheme for preparing the composite conductive agent, the method comprises the following steps:
(A) adding acetylene black and conductive graphite into an organic solvent and optional PVP according to a mass ratio of 1 (0.2-5), then adding into a dispersion disc of a high-speed stirrer, and dispersing for 2-3h under the condition of a rotating speed of 700-800rpm to obtain first composite conductive slurry;
(B) adding carbon nanofibers, carbon nanotubes and graphene into an organic solvent and optional PVP according to a mass ratio of 1 (0.2-5) to (0.2-5), then adding into a dispersion disc of a high-speed stirrer, and dispersing for 2 hours at a rotating speed of 2000rpm to obtain second composite conductive slurry;
(C) and mixing the first composite conductive paste and the second composite conductive paste to obtain the composite conductive paste, namely the composite conductive agent.
In the preferred embodiment, the rpm of step (A) is 700-800rpm, such as 700rpm, 725rpm, 750rpm, 770rpm, or 800 rpm.
Preferably, the organic solvent of step (a) is added so that the slurry has a solid content of 10% to 30%.
Preferably, the organic solvent of step (B) is added so that the solid content of the slurry is 7-8%.
Preferably, in the process of preparing the first composite conductive paste in the step (a), the method further comprises the step of modifying the nano aluminum powder before using the acetylene black, specifically: and mixing and stirring the acetylene black and the nano aluminum powder to obtain the acetylene black modified by the nano aluminum powder.
Preferably, the mass percentage of the nano aluminum powder is 5% based on 100% of the total mass of the acetylene black modified by the nano aluminum powder, and the mass percentage is the doping amount of the nano aluminum powder.
Preferably, in the process of preparing the first composite conductive paste in the step (a), a step of performing surface activation before using the acetylene black is further included, specifically: and (3) carrying out surface cleaning on the acetylene black by using acetone to obtain the acetylene black with the activated acetone surface.
Preferably, in the process of preparing the first composite conductive paste in step (a), a step of surface activation is further included before the conductive graphite is used, specifically: and cleaning the surface of the conductive graphite by using acetone to obtain the conductive graphite with the activated acetone surface.
In the preferred technical scheme, PVP is preferably added in the step (A) so as to be beneficial to forming the conductive paste with more uniform dispersion.
In the preferable technical scheme, PVP is preferably added in the step (B), the carbon nano tubes are preferably multi-layer carbon nano tubes, NMP is mixed into the nano carbon fibers, the multi-layer carbon nano tubes and the graphene under the condition, a certain amount of dispersant PVP is added, and the PVP is dispersed by a high-speed dispersing machine, so that the conductive slurry which is dispersed more uniformly can be obtained.
In the preferred technical scheme, the acetylene black and the conductive carbon black are dispersed together, the carbon nano tube and the carbon nano fiber are dispersed together, and the mode of dispersing the acetylene black and other substances and mixing the acetylene black and the carbon nano tube at last is more favorable for exerting the effect of improving the dispersion of the carbon nano tube, so that the conductive slurry which is more uniform and stable in dispersion is formed, the conductive performance of the positive plate is improved, the electrode polarization is reduced, the internal resistance of the battery is reduced, and the performance of the battery is improved.
In the preferred technical scheme, the step (A) and the step (B) are respectively mixed and respectively stirred at a specific rotating speed, so that two kinds of uniformly dispersed conductive slurry can be obtained, and compared with a mode of firstly mixing and then directly stirring, a mode of firstly respectively preparing the two kinds of slurry and then mixing is adopted, the obtained composite conductive slurry has large effect difference, and the result shows that: the conductive paste prepared by respectively preparing the two pastes and mixing the two pastes is better in point-line surface matching, and the omnibearing conductive network is more beneficial to improving the point-line surface matching and the point contact with the active material, so that the conductivity is improved.
As a further preferable technical solution for preparing the composite conductive agent of the present invention, the method comprises the steps of:
(A) cleaning and activating acetylene black and conductive graphite respectively with acetone to obtain acetone-activated acetylene black and acetone-activated conductive graphite;
mixing the acetylene black activated by acetone with the nano aluminum powder, and stirring to obtain nano aluminum powder modified acetylene black with the doping amount of the nano aluminum powder being 5%;
adding nano aluminum powder modified acetylene black and acetone activated conductive graphite into a mixed solution of NMP and PVP according to a mass ratio of 1 (0.2-5) to enable the solid content of the slurry to be 10% -30%, then adding the slurry into a dispersion disc of a high-speed stirrer, and dispersing for 2-3 hours at a rotating speed of 700-800rpm to obtain first composite conductive slurry;
(B) adding the carbon nanofibers, the multilayer carbon nanotubes and the graphene into NMP and PVP according to a mass ratio of 1 (0.2-5) to enable the solid content of the slurry to be 8%, then adding the slurry into a dispersion disc of a high-speed stirrer, and dispersing for 2 hours at a rotating speed of 2000rpm to obtain second composite conductive slurry;
(C) and mixing the first composite conductive paste and the second composite conductive paste to obtain the composite conductive paste, namely the composite conductive agent.
In the preferred technical scheme, acetone is used for carrying out surface cleaning and activation on the acetylene black and the conductive graphite, PVP is used as a dispersing agent to disperse the acetylene black and the conductive graphite activated by the acetone together with NMP, the activity of the composite conductive agent can be improved, the electric difference of a charging and discharging platform is reduced, and polarization is reduced. In addition, the preferable technical scheme cooperatively uses five rigid and flexible conductive particles activated by different methods, namely acetylene black modified by nano aluminum powder, acetone activated conductive graphite, a multilayer carbon nanotube, nano carbon fiber and graphene, and obtains the composite conductive slurry through two-step respective dispersion and final mixing, so that a conductive network structure in the conductive slurry is favorable for improving the point-line surface contact conductive effect, and when the conductive network structure is used for preparing a pole piece, the compaction density, the specific surface area and the electrolyte adsorption capacity of the pole piece can be improved, and the ionic conductivity of the pole piece is further improved.
In a third aspect, the present invention provides a cathode slurry, where the conductive agent in the cathode slurry is the composite conductive agent of the first aspect, and preferably the composite conductive slurry is composed of the first composite conductive slurry and the second composite conductive slurry.
Preferably, the positive electrode active material in the positive electrode slurry is a ternary positive electrode material.
The conductive agent in the anode slurry disclosed by the invention uses five conductive particles, namely acetylene black, conductive graphite, carbon nano tubes, carbon nanofibers and graphene, and the rigid particles and the flexible particles are matched in a proper amount, so that the compaction density of an anode plate, particularly a ternary-material anode plate, can be improved, the specific surface area and the electrolyte adsorption capacity are improved, and the ionic conductivity of the anode plate is further improved.
In a fourth aspect, the present invention provides a method for producing the positive electrode slurry according to the third aspect, the method comprising the steps of:
(1) mixing a binder and a solvent to prepare a glue solution;
(2) mixing the glue solution with a conductive agent and a positive active substance to obtain a mixed glue solution, controlling the solid content of the mixed glue solution to be 70-75%, and stirring to obtain positive slurry;
wherein the conductive agent in the step (2) is the composite conductive agent of the first aspect.
As a preferable technical scheme for preparing the anode slurry, the conductive agent in the step (2) is composite conductive slurry, and conductive particles in the composite conductive slurry are composed of acetylene black, conductive graphite, carbon nanofibers, carbon nanotubes and graphene.
More preferably, the conductive agent of step (2) is: the composite conductive paste is composed of a first composite conductive paste and a second composite conductive paste.
Preferably, the step (2) of mixing the glue solution, the conductive agent and the positive electrode active material comprises the following steps:
and mixing the glue solution with the first composite conductive paste, then mixing with the second composite conductive paste, and finally mixing with the positive active substance to obtain the mixed glue solution.
In the preferred technical scheme, the first composite conductive slurry of the conductive carbon black rigid conductive particles containing acetylene black is mixed firstly, and then is mixed with the second composite conductive slurry of the flexible conductive particles containing carbon nanofibers, carbon nanotubes, graphene and the like, so that a good conductive network can be formed more favorably, good point contact between the conductive particles and an active material can be realized, and the mixing mode is also more favorable for developing the effect of the acetylene black on improving the dispersion of the carbon nanotubes, thereby forming the conductive slurry which is more uniformly dispersed, improving the conductive performance of a positive plate, lightening the electrode polarization, reducing the internal resistance of a battery and improving the performance of the battery.
Preferably, the binder in step (1) is Polyvinylidene fluoride (PVDF).
Preferably, the solvent of step (1) is NMP.
Preferably, the mixing of the binder and the solvent in the step (1) is carried out under the stirring condition, the stirring speed is 700rpm, and the stirring time is 5-8 h.
Preferably, the mixing of the binder and the solvent in step (1) is performed under the stirring of a magnetic stirrer.
Preferably, the mass ratio of the positive electrode active material, the conductive agent and the binder in the step (2) is (95-96): 2-3): 2.
Preferably, the stirring in the step (2) is performed in a high-speed stirrer, and the rotating speed of the dispersion disc is 800 rpm.
Preferably, the stirring time of the step (2) is 4-5 h.
As a further preferable technical solution for preparing the cathode slurry according to the present invention, the method includes the steps of:
(1) mixing PVDF and NMP, and stirring for 5-8h at 700rpm in a magnetic stirrer to prepare a glue solution;
(2) mixing the glue solution with a first composite conductive slurry with a solid content of 10-30%, then mixing with a second composite conductive slurry with a solid content of 8%, finally mixing with a ternary positive electrode material to obtain a mixed glue solution, controlling the solid content of the mixed glue solution to be 70-75%, and stirring for 4-5h at 800rpm in a high-speed stirrer to obtain a positive electrode slurry;
the mass ratio of the ternary positive electrode material to the first composite conductive paste to the second composite conductive paste to the PVDF is 95:2:1: 2.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a novel composite conductive agent, which comprises rigid conductive particles of acetylene black and conductive graphite, and flexible carbon nanofibers, carbon nanotubes and graphene, and has excellent performance by using appropriate amounts of the five conductive particles.
The composite conductive agent disclosed by the invention has a good point-line-surface all-directional conductive network, and conductive particles in the composite conductive agent and active substances form larger contact points, so that the conductive performance of an electrode plate can be greatly improved, the polarization of the electrode plate is reduced, the internal resistance of a battery is reduced, and the performance of the battery is improved.
(2) The proper amount of the acetylene black added in the invention can improve the dispersibility of the carbon nano tube, thereby forming more uniformly dispersed conductive slurry, improving the conductive performance of the positive plate, lightening the electrode polarization, reducing the internal resistance of the battery and improving the performance of the battery.
(3) In the invention, acetone is adopted to carry out surface cleaning and activation on acetylene black and conductive carbon black, so that the activity of a conductive agent can be further improved in a synergistic manner, the electric difference of a charge-discharge platform is reduced, and the polarization is reduced; the modified acetylene black nano aluminum powder is further matched to modify, so that the activity of the conductive agent can be synergistically improved, more active sites can be provided, the stability of the conductive agent in air for long-term storage can be improved, and the dispersibility of the conductive agent in the anode slurry can be improved.
(4) The composite conductive agent is adopted to homogenize the anode material, so that the compaction density (the compaction density can be improved by more than 6% under the same pressure roller), the electrolyte adsorption capacity and the ionic conductivity of the anode plate can be improved. The rate capability and the cycle performance of a battery which is further assembled by preparing the positive electrode slurry by adopting the composite conductive agent are obviously improved.
Drawings
FIG. 1 is a graph comparing charge and discharge cycles at 0.5C for the products of examples 1-2 and comparative examples 1-2, with the abscissa being the number of cycles in units of times; the ordinate is the specific discharge capacity, and the unit is mAh/g;
FIG. 2 is a graph comparing charge and discharge cycles at 1C for the products of examples 1-2 and comparative examples 1-2, with the abscissa being the number of cycles in units of times; the ordinate is specific discharge capacity in mAh/g.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The material is mainly selected from: 523 ternary positive electrode material, 100-200 nm carbon nanofibers, carbon nanotubes, acetylene black, conductive graphite, graphene, HSV900 type PVDF and NMP.
Example 1:
the embodiment provides a composite conductive agent, and the preparation method of the composite conductive agent comprises the following specific processes:
1. preparation of acetylene Black, conductive graphite Mixed conductive agent (first composite conductive paste)
And (3) respectively cleaning the acetylene black and the conductive graphite by using acetone, and drying in a vacuum drying oven. Adding nano aluminum powder into acetylene black cleaned and dried by acetone, and uniformly stirring to obtain the acetylene black modified by the nano aluminum powder (the mass percent of the nano aluminum powder is 5% based on 100% of the total mass of the acetylene black modified by the nano aluminum powder).
Adding the mixed acetylene black (namely the acetylene black modified by the nano aluminum powder) and the conductive graphite into NMP according to the mass ratio of 1:0.5, wherein the solid content is 10-30%, dispersing for 2-3h by using a 700-plus-800 rpm high-speed stirrer (a dispersion disc), and placing into a glove box for later use.
2. Preparation of carbon nanofiber, carbon nanotube and graphene mixed conductive agent (second composite conductive paste)
Adding the carbon nanofibers, the carbon nanotubes and the graphene into an NMP solvent according to the mass ratio of 1:1:0.5, wherein the solid content is about 8%. Adding a high-speed stirrer (a dispersion disc) to disperse for 2h at 2000rpm, and placing into a glove box for later use.
3. Preparing PVDF glue solution:
according to the anode material: first composite conductive paste: second composite conductive paste: and weighing a proper amount of PVDF and NMP according to the mass ratio of 95:2:1:2 of PVDF. And dissolving PVDF in NMP, and putting the NMP into a magnetic stirrer at 700rpm for mixing for 5-8h to obtain PVDF glue solution.
4. Preparing positive electrode slurry:
according to the anode material: first composite conductive paste: second composite conductive paste: the PVDF is mixed according to the mass ratio of 95:2:1:2, the PVDF glue solution is fused, then the second composite conductive slurry is added, then the first composite conductive slurry is mixed, finally the anode material is added for mixing, the total solid content of the obtained mixed glue solution is controlled to be 70-75%, and the mixed glue solution is placed into a high-speed mixer (dispersion disc) to be mixed for about 4-5 hours at 800 rpm.
5. Making a buckle:
the prepared anode slurry is evenly coated on an aluminum foil, and is cut into an anode piece after being dried, and the anode piece is dried in vacuum for more than 10 hours at 110 ℃. Assembling 2032 button cell by using metal lithium sheet as cathode and electrolyte as fir electrolyte product in glove box, standing for 24h, and performing charge and discharge test at 25 deg.C and 3.0-4.3V.
Example 2:
the embodiment provides a composite conductive agent, and the preparation method of the composite conductive agent comprises the following specific processes:
1. preparation of acetylene Black, conductive graphite Mixed conductive agent (first composite conductive paste)
And (3) respectively cleaning the acetylene black and the conductive graphite by using acetone, and drying in a vacuum drying oven. Adding nano aluminum powder into acetylene black cleaned and dried by acetone, and uniformly stirring to obtain the acetylene black modified by the nano aluminum powder (the mass percent of the nano aluminum powder is 5% based on 100% of the total mass of the acetylene black modified by the nano aluminum powder).
Adding the mixed acetylene black (namely the acetylene black modified by the nano aluminum powder) and the conductive graphite into NMP according to the mass ratio of 1:1, wherein the solid content is 10-30%, dispersing for 2-3h by using a 700-plus-material 800rpm high-speed stirrer (a dispersion disc), and placing into a glove box for later use.
2. Preparation of carbon nanofiber, carbon nanotube and graphene mixed conductive agent (second composite conductive paste)
The carbon nanofibers, the carbon nanotubes and the graphene are added into an NMP solvent according to the mass ratio of 2:1:1, and the solid content is about 8%. Adding a high-speed stirrer (a dispersion disc) to disperse for 2h at 2000rpm, and placing into a glove box for later use.
3. Preparing PVDF glue solution:
according to the anode material: first composite conductive paste: second composite conductive paste: PVDF and NMP are weighed according to the mass ratio of 96:1.3:0.7: 2. And dissolving PVDF in NMP, and mixing in a magnetic stirrer at 700rpm for 5-8h to obtain PVDF glue solution.
4. Preparing positive electrode slurry:
according to the anode material: first composite conductive paste: second composite conductive paste: PVDF (polyvinylidene fluoride) is mixed according to the mass ratio of 96:1.3:0.7:2, PVDF glue solution is fused, second composite conductive slurry is added, first composite conductive slurry is mixed, and finally positive electrode material is added for mixing, so that the total solid content of the obtained mixed glue solution is controlled to be 70-75%, and the mixed glue solution is placed into a high-speed mixer (dispersion disc) and mixed for about 4-5 hours at 800 rpm.
The rest of the process and conditions were the same as in example 1.
Example 3:
the embodiment provides a composite conductive agent, and the preparation method of the composite conductive agent comprises the following specific processes:
1. preparation of acetylene Black, conductive graphite Mixed conductive agent (first composite conductive paste)
And (3) respectively cleaning the acetylene black and the conductive graphite by using acetone, and drying in a vacuum drying oven. Adding nano aluminum powder into acetylene black after being cleaned and dried by acetone, and uniformly stirring to obtain the acetylene black modified by the nano aluminum powder (the mass percent of the nano aluminum powder is 3.5% based on 100% of the total mass of the acetylene black modified by the nano aluminum powder).
Adding the mixed acetylene black (namely the acetylene black modified by the nano aluminum powder) and the conductive graphite into NMP according to the mass ratio of 1:0.5, wherein the solid content is 20%, dispersing for 3h by using a high-speed stirrer (a dispersion disc) at 800rpm, and placing into a glove box for later use.
2. Preparation of carbon nanofiber, carbon nanotube and graphene mixed conductive agent (second composite conductive paste)
The carbon nanofibers, the carbon nanotubes and the graphene are added into an NMP solvent according to the mass ratio of 1:5:3, and the solid content is about 7%. Adding a high-speed stirrer (a dispersion disc) to disperse for 2h at 2000rpm, and placing into a glove box for later use.
3. Preparing PVDF glue solution:
according to the anode material: first composite conductive paste: second composite conductive paste: PVDF and NMP are weighed according to the mass ratio of 96.5:1:0.5: 2. And dissolving PVDF in NMP, and placing the NMP into a magnetic stirrer at 700rpm for mixing for 5 hours to obtain PVDF glue solution.
4. Preparing positive electrode slurry:
according to the anode material: first composite conductive paste: second composite conductive paste: the PVDF is mixed with the first composite conductive slurry according to the mass ratio of 95:2:1:2, the PVDF is mixed with the second composite conductive slurry, and finally mixed with the anode material to obtain a mixed glue solution, the total solid content of the obtained mixed glue solution is controlled to be 70%, and the mixed glue solution is placed into a high-speed mixer (dispersion disc) to be mixed for about 5 hours at 800 rpm.
5. Making a buckle:
the prepared anode slurry is evenly coated on an aluminum foil, and is cut into an anode piece after being dried, and the anode piece is dried in vacuum for more than 10 hours at 110 ℃. Assembling 2032 button cell by using metal lithium sheet as cathode and electrolyte as fir electrolyte product in glove box, standing for 24h, and performing charge and discharge test at 25 deg.C and 3.0-4.3V.
Example 4:
the embodiment provides a composite conductive agent, and the preparation method of the composite conductive agent comprises the following specific processes:
1. preparation of acetylene Black, conductive graphite Mixed conductive agent (first composite conductive paste)
And (3) respectively cleaning the acetylene black and the conductive graphite by using acetone, and drying in a vacuum drying oven.
Adding the dried acetylene black (namely the acetylene black modified by the nano aluminum powder) and the conductive graphite into NMP according to the mass ratio of 1:3, wherein the solid content is 30%, dispersing for 3h by using a high-speed stirrer (a dispersion disc) at 800rpm, and placing into a glove box for later use.
2. Preparation of carbon nanofiber, carbon nanotube and graphene mixed conductive agent (second composite conductive paste)
Adding the carbon nanofibers, the carbon nanotubes and the graphene into an NMP solvent according to the mass ratio of 1:3:1, wherein the solid content is about 8%. Adding a high-speed stirrer (a dispersion disc) to disperse for 2h at 2000rpm, and placing into a glove box for later use.
3. Preparing PVDF glue solution:
according to the anode material: first composite conductive paste: and weighing a proper amount of PVDF and NMP according to the mass ratio of the PVDF to the second composite conductive slurry of 94:3:1: 2. And dissolving PVDF in NMP, and placing the NMP into a magnetic stirrer at 700rpm for mixing for 7h to obtain PVDF glue solution.
4. Preparing positive electrode slurry:
according to the anode material: first composite conductive paste: second composite conductive paste: the PVDF is mixed with the first composite conductive slurry according to the mass ratio of 95:2:1:2, the PVDF is mixed with the second composite conductive slurry, and finally mixed with the anode material to obtain a mixed glue solution, the total solid content of the obtained mixed glue solution is controlled to be 75%, and the mixed glue solution is placed into a high-speed mixer (dispersion disc) to be mixed for about 5 hours at 800 rpm.
5. Making a buckle:
the prepared anode slurry is evenly coated on an aluminum foil, and is cut into an anode piece after being dried, and the anode piece is dried in vacuum for more than 10 hours at 110 ℃. Assembling 2032 button cell by using metal lithium sheet as cathode and electrolyte as fir electrolyte product in glove box, standing for 24h, and performing charge and discharge test at 25 deg.C and 3.0-4.3V.
Example 5:
the embodiment provides a composite conductive agent, and the preparation method of the composite conductive agent comprises the following specific processes:
1. preparation of acetylene Black, conductive graphite Mixed conductive agent (first composite conductive paste)
Adding nano aluminum powder into acetylene black, and uniformly stirring to obtain the acetylene black modified by the nano aluminum powder (the mass percent of the nano aluminum powder is 5% based on 100% of the total mass of the acetylene black modified by the nano aluminum powder).
Adding the mixed acetylene black (namely the acetylene black modified by the nano aluminum powder) and the conductive graphite into NMP according to the mass ratio of 1:1, wherein the solid content is 10%, dispersing for 2h by using a high-speed stirrer (a dispersion disc) at 750rpm, and placing into a glove box for later use.
2. Preparation of carbon nanofiber, carbon nanotube and graphene mixed conductive agent (second composite conductive paste)
The carbon nanofibers, the carbon nanotubes and the graphene are added into an NMP solvent according to the mass ratio of 1:5:5, and the solid content is about 8%. Adding a high-speed stirrer (a dispersion disc) to disperse for 2h at 2000rpm, and placing into a glove box for later use.
3. Preparing PVDF glue solution:
according to the anode material: first composite conductive paste: second composite conductive paste: and weighing a proper amount of PVDF and NMP according to the mass ratio of 94:3:1:2 of PVDF. And dissolving PVDF in NMP, and placing the NMP into a magnetic stirrer at 700rpm for mixing for 7h to obtain PVDF glue solution.
4. Preparing positive electrode slurry:
according to the anode material: first composite conductive paste: second composite conductive paste: the PVDF is mixed according to the mass ratio of 95:2:1:2, the PVDF glue solution is fused, then the second composite conductive slurry is added, then the first composite conductive slurry is mixed, finally the anode material is added for mixing, the total solid content of the obtained mixed glue solution is controlled to be 75%, and the mixed glue solution is placed into a high-speed mixer (dispersion disc) to be mixed for about 5 hours at 800 rpm.
5. Making a buckle:
the prepared anode slurry is evenly coated on an aluminum foil, and is cut into an anode piece after being dried, and the anode piece is dried in vacuum for more than 10 hours at 110 ℃. Assembling 2032 button cell by using metal lithium sheet as cathode and electrolyte as fir electrolyte product in glove box, standing for 24h, and performing charge and discharge test at 25 deg.C and 3.0-4.3V.
Comparative example 1:
according to the anode material: conductive agent: PVDF is 96:2:2, and materials are weighed (the conductive agent is a carbon nano tube).
1. Preparation of carbon nanotube conductive agent
The carbon nanofibers were added to the NMP solvent at a solids content of about 8%. Adding a high-speed stirrer (a dispersion disc) for 2000 revolutions for dispersion for 2 hours, and then putting the mixture into a glove box for standby.
2. Preparation of PVDF glue solution
NMP is weighed according to the total solid content of about 70-75%, weighed PVDF is dissolved in NMP, and the obtained product is put into a magnetic stirrer 700 to be rotated and mixed for 5-8 h.
3. Preparation of Positive electrode slurry
And putting the weighed anode material and the conductive agent into the glue solution. The high speed mixer (disperser plate) 800 rotates for about 4-5 hours.
4. Manufacture buckle
And uniformly coating the prepared slurry on an aluminum foil, drying, cutting into a positive pole piece, and vacuum-drying at 110 ℃ for more than 10 h. Assembling 2032 button cell by using metal lithium sheet as cathode and electrolyte as fir electrolyte product in glove box, standing for 24h, and performing charge and discharge test at 25 deg.C and 3.0-4.3V.
Comparative example 2:
according to the anode material: conductive agent: PVDF is 96:2:2, and the material is weighed (acetylene black is used as a conductive agent).
1. Preparation of PVDF glue solution
Weighing NMP according to the solid content of about 70-75%, melting the weighed PVDF into the NMP, and putting the mixture into a magnetic stirrer 700 for mixing for 5-8 h.
2. Putting in a conductive agent
Putting the weighed conductive agent into the PVDF glue solution, transferring the PVDF glue solution into a high-speed stirrer (a dispersion disc) and dispersing the PVDF glue solution for 2 to 3 hours by using 700 and 800 turns.
3. Preparation of Positive electrode slurry
And putting the weighed anode material into the glue solution. The high speed mixer (disperser plate) 800 rotates for about 4-5 hours.
4. Manufacture buckle
And uniformly coating the prepared slurry on an aluminum foil, drying, cutting into a positive pole piece, and vacuum-drying at 110 ℃ for more than 10 h. Assembling 2032 button cell by using metal lithium sheet as cathode and electrolyte as fir electrolyte product in glove box, standing for 24h, and performing charge and discharge test at 25 deg.C and 3.0-4.3V.
FIG. 1 is a comparison graph of charge and discharge cycles at 0.5C for the products of examples 1-2 and comparative examples 1-2 (abscissa is cycle number in times; ordinate is specific discharge capacity in mAh/g), from which it can be seen that the specific discharge capacity of the examples is significantly better than that of the comparative examples, and the examples have no large jump in specific discharge capacity compared to that of the comparative examples. The conductive performance, polarization voltage and internal resistance of the slurry of the example are obviously superior to those of the comparative example.
FIG. 2 is a graph comparing the charge and discharge cycles of the products of examples 1-2 and comparative examples 1-2 at 1C (the abscissa is the number of cycles in times and the ordinate is the specific discharge capacity in mAh/g), and it can be seen that the specific discharge capacity of the same examples is significantly better than that of the comparative examples, and the specific discharge capacity of the examples is not greatly jumped as compared with that of the comparative examples. The conductive performance, polarization voltage and internal resistance of the slurry of the example are obviously superior to those of the comparative example.
The compacted density of the pole pieces of the examples was 3.2g/m under the same rolling conditions2While the comparative example can only reach 3.0g/m2An improvement of about 6 percentage points. The internal resistance to pull-in of the example was 52 milliohms, while the internal resistance to pull-in of the comparative example was 67 milliohms. Therefore, the addition of the composite conductive agent not only improves the compaction density of the pole piece, but also forms a point-line-surface conductive network, thereby greatly reducing the internal resistance of the battery.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (31)
1. A composite conductive agent is characterized in that the composite conductive agent is composite conductive slurry, the composite conductive slurry is composed of first composite conductive slurry and second composite conductive slurry, the first conductive slurry is slurry obtained by dispersing acetylene black and conductive graphite in an organic solvent according to the mass ratio of 1 (0.2-5), and the second composite conductive slurry is slurry obtained by dispersing carbon nanofibers, carbon nanotubes and graphene in the organic solvent according to the mass ratio of 1 (0.2-5) to (0.2-5);
the mass ratio of the first composite conductive paste to the second composite conductive paste is (1-3): 1; the solid content of the first composite conductive slurry is 10% -30%, and the solid content of the second composite conductive slurry is 7% -9%;
the acetylene black is acetylene black modified by nano aluminum powder and activated on the surface of acetone;
the conductive graphite is activated on the surface of acetone.
2. The composite conductive agent according to claim 1, wherein the first conductive paste is a paste obtained by dispersing acetylene black and conductive graphite in an organic solvent and polyvinylpyrrolidone (PVP) in a mass ratio of 1 (0.2-5).
3. The composite conductive agent of claim 1, wherein the second composite conductive paste is a paste obtained by dispersing the carbon nanofibers, the carbon nanotubes and the graphene in an organic solvent and PVP at a mass ratio of 1 (0.2-5) to (0.2-5).
4. The composite conductive agent according to claim 1, wherein the mass ratio of the acetylene black to the conductive graphite is 1:1.
5. The composite conductive agent according to claim 1, wherein the organic solvent is N-methylpyrrolidone NMP.
6. The composite conductive agent according to claim 1, wherein the conductive particles of the composite conductive paste are composed of acetylene black, conductive graphite, carbon nanofibers, carbon nanotubes, and graphene.
7. The composite conductive agent according to claim 1, wherein the solid content of the second composite conductive paste is 8%.
8. The composite conductive agent according to claim 1, wherein the mass ratio of the first composite conductive paste to the second composite conductive paste is 2: 1.
9. The composite conductive agent as claimed in claim 1, wherein the nano aluminum powder is 5% by mass based on 100% by mass of the acetylene black modified by the nano aluminum powder.
10. The composite conductive agent according to claim 1, wherein the diameter of the filamentous nanocarbon is 100nm to 200nm, and the aspect ratio is 100nm to 500 nm.
11. The composite conductive agent according to claim 1, wherein the carbon nanotube is a single-walled carbon nanotube and/or a multi-walled carbon nanotube.
12. The composite conductive agent according to claim 11, wherein the carbon nanotube is a multilayered carbon nanotube.
13. The method for preparing the composite conductive agent according to claim 1, comprising the steps of:
(A) cleaning acetylene black and conductive graphite respectively by using acetone, drying in a vacuum drying oven, adding nano aluminum powder into the acetylene black cleaned and dried by using the acetone, and uniformly stirring to obtain nano aluminum powder modified acetylene black;
adding acetylene black modified by nano aluminum powder and conductive graphite into an organic solvent and PVP according to the mass ratio of 1 (0.2-5), then adding into a dispersion disc of a high-speed stirrer, and dispersing for 2-3h under the condition of the rotating speed of 700-800rpm to obtain first composite conductive slurry;
(B) adding carbon nanofibers, carbon nanotubes and graphene into an organic solvent and PVP according to a mass ratio of 1 (0.2-5) to (0.2-5), then adding into a dispersion disc of a high-speed stirrer, and dispersing for 2 hours at a rotating speed of 2000rpm to obtain second composite conductive slurry;
(C) and mixing the first composite conductive paste and the second composite conductive paste to obtain the composite conductive paste, namely the composite conductive agent.
14. The method of claim 13, wherein the organic solvent is NMP.
15. The method of claim 13, wherein the organic solvent of step (a) is added so that the slurry has a solids content of 10% to 30%.
16. The method of claim 13, wherein the organic solvent of step (B) is added to provide a slurry solids content of 7% to 8%.
17. The method as claimed in claim 13, wherein the mass percentage of the nano aluminum powder is 5% based on 100% of the total mass of the acetylene black modified by the nano aluminum powder.
18. A positive electrode slurry, wherein the conductive agent in the positive electrode slurry is the composite conductive agent according to any one of claims 1 to 12.
19. The positive electrode paste according to claim 18, wherein the positive electrode paste comprises a composite conductive paste composed of the first composite conductive paste and the second composite conductive paste.
20. The positive electrode slurry according to claim 18, wherein the positive electrode active material in the positive electrode slurry is a ternary positive electrode material.
21. The method for producing positive electrode slurry according to claim 18, characterized by comprising the steps of:
(1) mixing a binder and a solvent to prepare a glue solution;
(2) mixing the glue solution with a conductive agent and a positive active substance to obtain a mixed glue solution, controlling the solid content of the mixed glue solution to be 70-75%, and stirring to obtain positive slurry;
wherein the conductive agent in the step (2) is the composite conductive agent according to any one of claims 1 to 10.
22. The method according to claim 21, wherein the conductive agent in the step (2) is a composite conductive paste, and the conductive particles in the composite conductive paste are composed of acetylene black, conductive graphite, carbon nanofibers, carbon nanotubes and graphene.
23. The method of claim 21, wherein the conductive agent of step (2) is: the composite conductive paste is composed of a first composite conductive paste and a second composite conductive paste.
24. The method according to claim 21, wherein the step (2) of mixing the glue solution with the conductive agent and the positive active material comprises:
and mixing the glue solution with the first composite conductive paste, then mixing with the second composite conductive paste, and finally mixing with the positive active substance to obtain the mixed glue solution.
25. The method of claim 21, wherein the binder of step (1) is polyvinylidene fluoride (PVDF).
26. The method of claim 21, wherein the solvent of step (1) is NMP.
27. The method according to claim 21, wherein the mixing of the binder and the solvent in the step (1) is performed under stirring conditions, wherein the stirring speed is 700rpm, and the stirring time is 5-8 h.
28. The method of claim 21, wherein the step (1) of mixing the binder and the solvent is performed with agitation by a magnetic stirrer.
29. The method according to claim 21, wherein the mass ratio of the positive electrode active material, the conductive agent and the binder in the step (2) is (95-96): 2-3): 2.
30. The method of claim 21, wherein the stirring of step (2) is performed in a high-speed stirrer, and the rotation speed of the dispersion plate is 800 rpm.
31. The method according to claim 21, wherein the stirring time in the step (2) is 4-5 h.
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