CN107331440B - A kind of carbon nanotube conducting slurry, the preparation method of positive electrode and lithium battery - Google Patents
A kind of carbon nanotube conducting slurry, the preparation method of positive electrode and lithium battery Download PDFInfo
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- CN107331440B CN107331440B CN201710517742.5A CN201710517742A CN107331440B CN 107331440 B CN107331440 B CN 107331440B CN 201710517742 A CN201710517742 A CN 201710517742A CN 107331440 B CN107331440 B CN 107331440B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 82
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 82
- 239000002002 slurry Substances 0.000 title claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 69
- 239000006258 conductive agent Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000000853 adhesive Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 210000004027 cell Anatomy 0.000 abstract description 8
- 230000001737 promoting effect Effects 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 210000003850 cellular structure Anatomy 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910004764 HSV900 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of carbon nanotube conducting slurry, the preparation method of positive electrode and lithium batteries, belong to technical field of lithium ion.The characteristics of embodiment of the present invention is uniform using carbon nanotube, periodical cellular structure, carbon nanotube is fabricated to slurries as conductive agent and introduces positive electrode, it is well dispersed in carbon nanotube in cell positive material, to improve the performances such as cycle performance, high-power output and the quick charge of battery, avoids and carbon nanotube is directly used as agglomeration traits caused by positive electrode.In addition, the embodiment of the present invention when preparing lithium battery, controls compacted density, reduction battery volume, the capacity for promoting battery core from integrated structure, to promote the energy density of battery.
Description
Technical field
The present invention relates to technical field of lithium ion, in particular to the system of a kind of carbon nanotube conducting slurry, positive electrode
Preparation Method and lithium battery.
Background technique
2017, country for new-energy automobile financial subsidies, will be subsidized by energy density, using course continuation mileage as
Necessary index.Government encourages using and promoting for the advanced technologies such as high-energy density, vehicle lightweight, while to the cost of battery
Higher requirements are also raised for control.In conjunction with the technical requirements in subsidy for energy-type cells, the energy density of battery is improved
It is the critical issue of each electric car enterprises pay attention.
The ternary battery that energy density is big and performance is good needs the performance of higher gram volume, better battery structure and more
Excellent functional material, therefore cost can be higher.In the prior art by the way that ternary material and cheap LiMn2O4, cobalt is sour
The materials such as lithium are blended, and can effectively reduce the cost of battery.In addition, increasing the big electricity of battery to reduce the internal resistance of battery
Discharge capability is flowed, the cycle life of battery is improved, carbon nanotube, conductive black, conductive stone are added in the positive electrode of battery
The conductive agents such as ink, carbon nano-tube fibre, wherein carbon nanotube belongs to mesoporous material, with periodic arrangement duct, it is uniform and
The features such as various skeleton of adjustable aperture structure, high-specific surface area, composition in 2-50nm.When being used as electrode material, carbon
The interstitial space of nanotube can be used as cushion space, to reduce destruction of the material volume variation to electrode structure, be conducive to mention
High circulation performance；And carbon nanotube pore wall thickness it is uniform and be less than 20nm, make lithium ion without over long distances diffusion can reach
The activity space of electrode material；Duct can be used as the transmission channel of electrolyte simultaneously, and lithium ion is enable quickly to reach in electrode
Portion is conducive to high-power output and quick charge.
In the implementation of the present invention, the inventors discovered that in the prior art the prior art has at least the following problems: since carbon is received
Mitron nanoscale size and biggish specific surface area cause it to be easy to gather into bundles in the solution to reunite, cannot make
Carbon nanotube is well dispersed in cell positive material, increases the internal resistance of battery, reduces the discharge capability of battery, in turn
Influence the energy density of battery.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of carbon nanotube conducting slurry, positive electrode and its lithium electricity
The preparation method in pond.
Specifically, including technical solution below:
A kind of preparation method of carbon nanotube conducting slurry, comprising the following steps:
Step 1a) vacuum bakeout carbon nanotube；
Step 2a) polyvinyl alcohol and N-Methyl pyrrolidone and the carbon nanotube are mixed, obtain carbon nanotube
Conductive paste.
Wherein, the carbon nanotube, the weight ratio of the polyvinyl alcohol and the N-Methyl pyrrolidone are as follows: 100:28:
2；Or are as follows: 100:20:2；And the solid content of the N-Methyl pyrrolidone is 60%~80%.
A kind of preparation method of positive electrode, comprising the following steps:
Step 1b) the main powder material of baking, adhesive and conductive agent；
Step 2b) Kynoar solution, N-Methyl pyrrolidone and described adhesive are mixed, it obtains mixing molten
Agent；Carbon nanotube conducting described in claim 1 slurry is mixed with the mixed solvent, it is mixed to obtain carbon nanotube conducting slurry
Material；
Step 3b) carbon nanotube conducting slurry mixing and the conductive agent are mixed, obtain conductive agent mixing；
Step 4b) the main powder material is added in three times in the conductive agent mixing, it is mixed, obtains anode
Material.
Preferably, the main powder material is made of ternary material and LiMn2O4；And the ternary material and the LiMn2O4
Weight ratio are as follows: (70-80wt%): (20-30wt%).
A kind of lithium battery, including positive plate, negative electrode tab, diaphragm, electrolyte and aluminum plastic film；The positive plate with it is above-mentioned just
Pole material is coated, wherein the main powder material, the conductive agent and the carbon nanotube in the positive electrode and
The weight ratio of described adhesive are as follows: (85-99%): (0.1-5%): (0.5-10%).
Preferably, the negative electrode material of the negative electrode tab is water system carbon.
Preferably, the coating weight of the positive electrode is (30-50) mg/cm2, positive roll-in with a thickness of (0.1-0.5) mm,
Positive compacted volume density is (2.0-6.0) g/cm3；The coating weight of the negative electrode material is (10-30) mg/cm2, cathode roll-in
With a thickness of (0.1-0.5) mm, cathode compacted volume density is (1.0-5.0) g/cm3。
Preferably, the positive electrode and the capacity ratio of the negative electrode material are 1:(1.05-1.5).
Preferably, the diaphragm includes ceramic diaphragm, the ceramic diaphragm with a thickness of 20-35 μm.
Preferably, the electrolyte is function type eletrolysis solution.
Technical solution provided in an embodiment of the present invention the utility model has the advantages that providing a kind of carbon nanotube conducting slurry, positive material
The preparation method of material and its lithium battery.The characteristics of embodiment of the present invention is uniform using carbon nanotube, periodical cellular structure, by carbon
Nanotube is fabricated to slurries as conductive agent and introduces positive electrode, and carbon nanotube is allow to be well dispersed in cell positive material
In, the performances such as cycle performance, high-power output and the quick charge of battery are improved, avoids and carbon nanotube is directly used as anode
Agglomeration traits caused by material.
In addition, the embodiment of the present invention when preparing lithium battery, controls compacted density from integrated structure, reduces cell body
Product, the capacity for promoting battery core, to promote the energy density of battery.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, below in conjunction with attached drawing to embodiment of the present invention make into
One step it is described in detail.Unless otherwise defined, all technical terms used in the embodiment of the present invention all have and art technology
The normally understood identical meaning of personnel.
The present invention provides a kind of preparation method for positive electrode in lithium battery, and for the one of positive electrode coating
The preparation method of kind carbon nanotube conducting slurry, illustrates the present invention below in conjunction with two embodiments.
Embodiment 1
The preparation of carbon nanotube conducting slurry:
Step 1a) vacuum bakeout carbon nanotube；
Powder prebake conditions: by 120 DEG C of carbon nanotube, -0.08MPa vacuum bakeout 2h, last closing temperature keeps vacuum,
It is cooled to 60 DEG C of taking-ups.
Step 2a) polyvinyl alcohol and N-Methyl pyrrolidone and the carbon nanotube are mixed, obtain carbon nanotube
Conductive paste.
Mixing: by 1000.0g carbon nanotube, (NMP is molten for 280g polyvinyl alcohol (dispersing agent) and 20g N-Methyl pyrrolidone
Agent) mixed low speed stirring 30 minutes, obtain stable carbon nanotube conducting slurry.
In above-mentioned carbon nanotube conducting slurry, the weight ratio of carbon nanotube, polyvinyl alcohol and N-Methyl pyrrolidone are as follows:
100:28:2；And the solid content of N-Methyl pyrrolidone is 60%~80%.Carbon nanotube is fabricated to slurries as conductive agent
Positive electrode is introduced, carbon nanotube is well dispersed in cell positive material, improves cycle performance, the big function of battery
The performances such as rate output and quick charge, avoid carbon nanotube being directly used as agglomeration traits caused by positive electrode.
The preparation of positive electrode:
Step 1b) the main powder material of baking, adhesive and conductive agent；
Specifically, the main powder material of 1000g is toasted 4 hours, 15g adhesive, 16g conductive agent vacuum at a temperature of 120 DEG C
Baking 2 hours, all of above temperature of charge drops to 45 DEG C or less rears and can be taken off, and thus obtains spare main powder material, bonding
Agent and conductive agent；
Wherein, main powder material is made of ternary material and LiMn2O4 (and/or cobalt acid lithium), by by ternary material and price
The materials such as cheap LiMn2O4, cobalt acid lithium are blended, and can be used for making the ternary battery that energy density is big and performance is good, while effectively
The cost of ground reduction battery.Preferably, main powder material is formed by ternary material and LiMn2O4, and ternary material and LiMn2O4
Weight proportion is 80wt%:20wt%, it is highly preferred that Shenzhen proud son of heaven (532) profile material can be selected in ternary material, LiMn2O4 can be
New positive lithium industry MH-3 material；And further, HSV900 can be selected in adhesive, and Super P (SP) conductive agent can be selected in conductive agent.
Step 2b) Kynoar solution, N-Methyl pyrrolidone and described adhesive are mixed, it obtains mixing molten
Agent；The carbon nanotube conducting slurry of above-mentioned preparation is mixed with the mixed solvent, obtains carbon nanotube conducting slurry mixing；
Specifically, 55 DEG C of heat recirculated water are opened in advance, by the 160.413g Kynoar solution weighed up (PVDF solution)
It is added in tank and is mixed with 110g N-Methyl pyrrolidone, then the 15g adhesive prepared in step 1b) is added in tank, low speed stirs
It mixes 20 minutes, it is spare to obtain mixed solvent；Then the carbon nanotube conducting slurry of the above-mentioned preparation of 230g is added in tank, it is molten with mixing
Agent is further mixed, and first stirs at low speed 20 minutes, then vacuumize, and continues high-speed stirred 3 hours, obtains carbon nanotube conducting
Starch mixing.
Step 3b) carbon nanotube conducting slurry mixing and the conductive agent are mixed, obtain conductive agent mixing；
Specifically, 0.5 hour open cycle cooling water can be shifted to an earlier date, the 16g conductive agent prepared in step 1b) is added in tank,
It is mixed with carbon nanotube conducting slurry mixing, stirs at low speed 20 minutes, scrape wall, moderate-speed mixer 2-3 hours, vacuumize, and mistake
Wall is scraped in journey several times, is observed dispersity 1 time, is obtained conductive agent mixing；
Wherein, " scraping wall " on the one hand can prevent waste of material, on the other hand since each material is all according to certain ratio
What example measured, scraping wall can be such that material does not end up on inner wall as far as possible, guarantee the proportion speed of material.Although and sometimes stirring when
Between arrive, but if slurry dispersion it is bad, will affect subsequent coating, thus in this process also need to observe slurry point
Bulk state, with guarantee prepared slurry fluidity it is good, without particle, free from admixture, bubble-free.
Step 4b) the main powder material is added in three times in the conductive agent mixing, it is mixed, obtains anode
Material.
Specifically, the main powder material of 1000g prepared in step 1b) is added in tank according to the sequence of weight ratio 5:3:2
It is mixed, stirs at low speed every time 20 minutes with conductive agent mixing；After twenty minutes, can opening scrapes wall, takes out for last time charging stirring
Vacuum, high-speed stirred 4.5 hours, then stir at low speed 0.5 hour；
It is down in critical field to slurry temperature, for example, summer temperature are as follows: 28 ± 5 DEG C；Winter temperature: 18 ± 5 DEG C；So
After detect slurry viscosity, for example, the range of qualified viscosity is between 6000~12000mPa.S, when detecting viscosity, if do not conformed to
Lattice can be properly added solvent；Again 0.5h is stirred at low speed, slurry viscosity is adjusted, is finally reached expected viscosity；It refilters, is sieved,
Obtain the positive electrode (slurry) for coating.
When preparing lithium battery, positive plate is prepared with positive electrode (slurry) coating of above-mentioned preparation, wherein anode slurry
When material coating, coated face density is (37.0 ± 0.4) mg/cm2, with a thickness of (0.130 ± 0.003) mm, compacted volume is close for roll-in
Degree is (3.2 ± 0.4) g/cm3.Cathode coated face density is (18.5 ± 0.3) mg/cm2, roll-in is with a thickness of (0.140 ± 0.003)
Mm, compacted volume density are (1.47 ± 0.3) g/cm3。
Wherein, the membrane thicknesses in lithium battery can be 29 μm of coating diaphragms.Electrolyte dosage is 33g/.
Embodiment 2
The preparation of carbon nanotube conducting slurry:
Step 1a) vacuum bakeout carbon nanotube；
Powder prebake conditions: by 120 DEG C of carbon nanotube, -0.08MPa vacuum bakeout 2h, last closing temperature keeps vacuum,
It is cooled to 60 DEG C of taking-ups.
Step 2a) polyvinyl alcohol and N-Methyl pyrrolidone and the carbon nanotube are mixed, obtain carbon nanotube
Conductive paste.
Mixing: by 1000.0g carbon nanotube, (NMP is molten for 200g polyvinyl alcohol (dispersing agent) and 20g N-Methyl pyrrolidone
Agent) mixed low speed stirring 30 minutes, obtain stable carbon conductive nano slurry.
In above-mentioned carbon nanotube conducting slurry, the weight ratio of carbon nanotube, polyvinyl alcohol and N-Methyl pyrrolidone are as follows:
100:20:2；And the solid content of N-Methyl pyrrolidone is 60%~80%.Carbon nanotube is fabricated to slurries as conductive agent
Positive electrode is introduced, carbon nanotube is well dispersed in cell positive material, improves cycle performance, the big function of battery
The performances such as rate output and quick charge, avoid carbon nanotube being directly used as agglomeration traits caused by positive electrode.
The preparation of positive electrode:
Step 1b) the main powder material of baking, adhesive and conductive agent；
Specifically, the main powder material of 1000g is toasted 4 hours, 15g adhesive, 16g conductive agent vacuum at a temperature of 120 DEG C
Baking 2 hours, all of above temperature of charge drops to 45 DEG C or less rears and can be taken off, and thus obtains spare main powder material, bonding
Agent and conductive agent；
Wherein, main powder material is made of ternary material and LiMn2O4 (and/or cobalt acid lithium), by by ternary material and price
The materials such as cheap LiMn2O4, cobalt acid lithium are blended, and can be used for making the ternary battery that energy density is big and performance is good, while effectively
The cost of ground reduction battery.Preferably, form main powder material by ternary material and two kinds of LiMn2O4s, and preferably, ternary material
The weight proportion of material and two kinds of LiMn2O4s is 70wt%:10wt%:10wt%, it is highly preferred that Shenzhen day can be selected in ternary material
Proud (532) profile material, LiMn2O4 can be new positive lithium industry MH-3 material and Jin Heyuan-MSL-LMO2-JHY material；And further
HSV900 can be selected in ground, adhesive, and Super P (SP) conductive agent can be selected in conductive agent.
Step 2b) Kynoar solution, N-Methyl pyrrolidone and described adhesive are mixed, it obtains mixing molten
Agent；The carbon nanotube conducting slurry of above-mentioned preparation is mixed with the mixed solvent, obtains carbon nanotube conducting slurry mixing；
Specifically, 55 DEG C of heat recirculated water are opened in advance, and the 160g Kynoar solution weighed up (PVDF solution) is added
It is mixed in tank with 430g N-Methyl pyrrolidone, then the 15g adhesive prepared in step 1b) is added in tank, stir at low speed 20
Minute, it is spare to obtain mixed solvent；The carbon nanotube conducting slurry of the above-mentioned preparation of 350g is added in tank, it is further with mixed solvent
It is mixed, first stirs at low speed 20 minutes, then vacuumize, continue high-speed stirred 3 hours, obtain carbon nanotube conducting slurry mixing.
Step 3b) carbon nanotube conducting slurry mixing and the conductive agent are mixed, obtain conductive agent mixing；
Specifically, 0.5 hour open cycle cooling water can be shifted to an earlier date, the 16g conductive agent prepared in step 1b) is added in tank,
It is mixed with carbon nanotube conducting slurry mixing, stirs at low speed 20 minutes, scrape wall, moderate-speed mixer 2-3 hours, vacuumize, and mistake
Wall is scraped in journey several times, is observed dispersity 1 time, is obtained conductive agent mixing；
Step 4b) the main powder material is added in three times in the conductive agent mixing, it is mixed, obtains anode
Material.
Specifically, the main powder material of 1000g prepared in step 1b) is added in tank according to the sequence of weight ratio 5:3:2
It is mixed, stirs at low speed every time 20 minutes with conductive agent mixing；After twenty minutes, can opening scrapes wall, takes out for last time charging stirring
Vacuum, high-speed stirred 4.5 hours, then stir at low speed 0.5 hour；
It is down in critical field to slurry temperature, detects slurry viscosity；It stirs at low speed again 0.5 hour.It refilters, is sieved,
Obtain the positive electrode (slurry) for coating.
When preparing lithium battery, positive plate is prepared with positive electrode (slurry) coating of above-mentioned preparation, wherein anode slurry
When material coating, coated face density is (37.0 ± 0.4) mg/cm2, with a thickness of (0.140 ± 0.003) mm, compacted volume is close for roll-in
Degree is (3.5 ± 0.4) g/cm3.Cathode coated face density is (18.5 ± 0.3) mg/cm2, roll-in is with a thickness of (0.140 ± 0.003)
Mm, compacted volume density are (1.5 ± 0.3) g/cm3。
Wherein, the membrane thicknesses in lithium battery can be 24 μm of coating diaphragms.Electrolyte dosage is 34g/.
The carbon nanotube conducting slurry and positive electrode prepared in based on the above embodiment, the present invention also provides a kind of lithium electricity
Pond, the lithium battery include positive plate, negative electrode tab, diaphragm, electrolyte and aluminum plastic film；Positive plate uses the slurries of above-mentioned positive electrode
It is coated, wherein the weight ratio of main powder material, conductive agent and carbon nanotube and adhesive in the slurries of positive electrode
Are as follows: (85-99%): (0.1-5%): (0.5-10%).Carbon nanotube production is slurried lithium battery provided in an embodiment of the present invention
Liquid introduces positive electrode as conductive agent, is well dispersed in carbon nanotube in cell positive material, improves battery
The performances such as cycle performance, high-power output and quick charge, avoid carbon nanotube being directly used as group caused by positive electrode
Poly- problem.
In above-mentioned lithium battery, the negative electrode material of pole piece is water system carbon.
In above-mentioned lithium battery, the coating weight of positive electrode is (30-50) mg/cm2, positive roll-in is with a thickness of (0.1-
0.5) mm, positive compacted volume density are (2.0-6.0) g/cm3；The coating weight of negative electrode material is (10-30) mg/cm2, cathode roller
For pressure with a thickness of (0.1-0.5) mm, cathode compacted volume density is (1.0-5.0) g/cm3.Lithium battery provided in an embodiment of the present invention
Into one by the compacted density of control positive plate and negative plate, the capacity for reducing battery volume, promoting battery core, to promote battery
Energy density.
In above-mentioned lithium battery, the capacity ratio of positive electrode and negative electrode material is 1:(1.05-1.5)；The capacity of cathode
It will be with respect to positive maximum, to prevent excessive lithium metal from generating Li dendrite in cathode deposition.
In above-mentioned lithium battery, diaphragm includes ceramic diaphragm, ceramic diaphragm with a thickness of 20-35 μm.
In above-mentioned lithium battery, electrolyte is function type eletrolysis solution, which can be low temperature resistant or resistance to
The electrolyte of high temperature, for example for TC-02 be low temperature multiplying power electrolyte, to adapt to requirement of the low temperature environment to battery.
The characteristics of embodiment of the present invention is uniform using carbon nanotube, periodical cellular structure, carbon nanotube production is slurried
Liquid introduces positive electrode as conductive agent, is well dispersed in carbon nanotube in cell positive material, improves battery
The performances such as cycle performance, high-power output and quick charge, avoid carbon nanotube being directly used as group caused by positive electrode
Poly- problem.In addition, the embodiment of the present invention is when preparing lithium battery, controlled from integrated structure compacted density, reduce battery volume,
The capacity for promoting battery core, to promote the energy density of battery.
The above is merely for convenience of it will be understood by those skilled in the art that technical solution of the present invention, not to limit
The present invention.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (9)
1. a kind of preparation method of carbon nanotube conducting slurry, which is characterized in that include the following steps
Step 1a) vacuum bakeout carbon nanotube；
Step 2a) polyvinyl alcohol and N-Methyl pyrrolidone and the carbon nanotube are mixed, obtain carbon nanotube conducting
Slurry；
Wherein, the carbon nanotube, the weight ratio of the polyvinyl alcohol and the N-Methyl pyrrolidone are as follows: 100:28:2；Or
Are as follows: 100:20:2；
And the solid content of the N-Methyl pyrrolidone is 60% ~ 80%.
2. a kind of preparation method of positive electrode, which is characterized in that include the following steps
Step 1b) the main powder material of baking, adhesive and conductive agent；
Step 2b) Kynoar solution, N-Methyl pyrrolidone and described adhesive are mixed, obtain mixed solvent；
Carbon nanotube conducting described in claim 1 slurry is mixed with the mixed solvent, obtains carbon nanotube conducting slurry mixing；
Step 3b) carbon nanotube conducting slurry mixing and the conductive agent are mixed, obtain conductive agent mixing；
Step 4b) the main powder material is added in three times in the conductive agent mixing, it is mixed, obtains positive material
Material.
3. preparation method according to claim 2, which is characterized in that the main powder material is by ternary material and LiMn2O4 group
At；And the weight ratio of the ternary material and the LiMn2O4 are as follows: (70-80wt%): (20-30wt%).
4. a kind of lithium battery, including positive plate, negative electrode tab, diaphragm, electrolyte and aluminum plastic film；It is characterized in that, the positive plate
It is coated using the positive electrode that preparation method according to claim 2 is prepared, wherein in the positive electrode
The main powder material, the conductive agent and the carbon nanotube and described adhesive weight ratio are as follows: (85-99%):
(0.1-5%): (0.5-10%).
5. lithium battery according to claim 4, which is characterized in that the negative electrode material of the negative electrode tab is water system carbon.
6. lithium battery according to claim 5, which is characterized in that the coating weight of the positive electrode is (30-50) mg/
cm2, with a thickness of (0.1-0.5) mm, positive compacted volume density is (2.0-6.0) g/cm for positive roll-in3；The negative electrode material
Coating weight is (10-30) mg/cm2, with a thickness of (0.1-0.5) mm, cathode compacted volume density is (1.0-5.0) g/ for cathode roll-in
cm3。
7. lithium battery according to claim 5, which is characterized in that the capacity ratio of the positive electrode and the negative electrode material
For 1:(1.05-1.5).
8. lithium battery according to claim 4, which is characterized in that the diaphragm includes ceramic diaphragm, the ceramic diaphragm
With a thickness of 20-35 μm.
9. lithium battery according to claim 4, which is characterized in that the electrolyte is function type eletrolysis solution.
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| CN109713308B (en) * | 2018-12-19 | 2022-04-05 | 浙江中科立德新材料有限公司 | CNT-containing aqueous lithium battery slurry and preparation method thereof |
| CN110190249A (en) * | 2019-04-19 | 2019-08-30 | 合肥国轩高科动力能源有限公司 | A kind of conjunction paste-making method of silicon-carbon cathode |
| RU2749904C1 (en) * | 2020-10-19 | 2021-06-18 | МСД Текнолоджис С.а.р.л. | Method for preparing anode paste for lithium-ion battery, anode paste, method for manufacture of anode (variants), anode (variants) and lithium-ion battery (variants) |
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| CN103066296A (en) * | 2012-12-20 | 2013-04-24 | 深圳华粤宝电池有限公司 | Lithium ion battery electrode slice, preparation method thereof and purpose thereof |
| CN103579668A (en) * | 2013-11-22 | 2014-02-12 | 江苏风迅新能源科技有限公司 | High-voltage and high-energy density lithium ion battery and preparation method thereof |
| CN103886932A (en) * | 2014-03-25 | 2014-06-25 | 深圳市纳米港有限公司 | Carbon nano tube electric conduction slurry and preparation method and application thereof |
| CN105406070A (en) * | 2015-12-18 | 2016-03-16 | 山东精工电子科技有限公司 | Preparation method of lithium ion battery positive pole size |
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| CN103066296A (en) * | 2012-12-20 | 2013-04-24 | 深圳华粤宝电池有限公司 | Lithium ion battery electrode slice, preparation method thereof and purpose thereof |
| CN103579668A (en) * | 2013-11-22 | 2014-02-12 | 江苏风迅新能源科技有限公司 | High-voltage and high-energy density lithium ion battery and preparation method thereof |
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