CN103346318A - Li-ion positive electrode slurry and preparation method thereof - Google Patents
Li-ion positive electrode slurry and preparation method thereof Download PDFInfo
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Abstract
The invention provides a Li-ion positive electrode slurry and a preparation method thereof. The preparation method comprises the following steps of: mixing lithium iron phosphate and dry inorganic conductive agent powder, wherein uniform mixing is judged by randomly sampling and measuring the resistance value of the powder, and is considered to be achieved when the difference of the resistance value of each sample powder is less than 5%; then adding PVDF (Polyvinylidene Fluoride) colloidal fluid into the mixture step by step; finally regulating the viscosity of the slurry by utilizing 1-Methyl-2-pyrrolidinone, thereby obtaining the Li-ion positive electrode slurry. The viscosity of the Li-ion positive electrode slurry is 3000-5000cps, and the Li-ion positive electrode slurry comprises 1-methyl-2-pyrrolidinone, as well as lithium iron phosphate, polyvinylidene fluoride and the inorganic conductive agent which are at a mass ratio of (85-95):(3-8):(2-10). According to the preparation method, whether the inorganic conductive agent is uniformly dispersed in lithium iron phosphate is determined by a method of randomly sampling dry powder, mixing samples and measuring the resistance values, and meanwhile, the PVDF colloidal fluid is added step by step in a substep slurry preparation process, so that the conventional thought of firstly mixing solid materials and adding the colloidal fluid in one step in a slurry preparation process in the field is broken through, and a favorable slurry preparation effect is achieved.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly a kind of lithium ion anode slurry and preparation method thereof.
Background technology
Lithium is the lightest element in the metal, and electrode potential is-3.045V, is the most negative in a metallic element element.Therefore receive chemical power source scientific worker's very big concern for a long time.The situation of taking off embedding of lithium ion from the material with carbon element lattice occurs in the electrode potential (than the lithium electrode current potential just) near lithium metal, and LiCoO
2The electrode potential of anodal reaction is (lithium electrode relatively) about about 4.0V, and therefore this novel storage battery has high operating voltage and high specific energy.Has low self-discharge rate in addition, long circulation life, memory-less effect and characteristics such as pollution-free.
Lithium ion battery anode glue size generally is uniformly dispersed by anode active material of lithium ion battery, conductive agent, binding agent and dispersant and forms.Slurry system belongs to high thickness solid-liquid two-phase suspension, and electrode slurry mixing dispersing technology is the important step that lithium battery is produced.In electrode slurry, the dispersiveness of graininess active material and uniformity directly influence lithium ion in the motion of battery two interpolars.
In the application process of reality, although people have recognized the importance of homogenate process, and process for refining flow process in process of production.But because amount is bigger in the production process, some tiny problems can be covered, and can accelerate the effect of homogenate as vacuum stirring and temperature control, thereby be unfavorable for obtaining high-quality anode sizing agent.
With regard to anode sizing agent preparation technology, major part is all continued to use traditional preparation technology, this technology is played glue with binding agent and solvent earlier, then the colloid of preparation is added in the mixture of positive active material and conductive agent and stir, or mixture added in the colloid prepare stir, vacuumize after stirring, discharging then, sieve, make anode sizing agent.Simple, the easy row of this preparation technology's flow process, but following deficiency also had: 1) because the difference of positive electrode and conductive agent granularity, volume density etc. causes the uniformity of slurry bad; 2) conductivity of slurry is bad, and conductive agent is reunited easily; 3) stability of slurry is bad, and slurry is placed sedimentation easily after 2-5 hour.
Summary of the invention
The object of the invention provide a kind of evenly, the lithium ion anode slurry of conductivity and good stability and preparation method thereof.
In order to achieve the above object, the preparation method of lithium ion anode slurry of the present invention comprises the steps:
1) by (85-95): (3-8): mass ratio (2-10) takes by weighing LiFePO4, Kynoar and inorganic conductive agent respectively;
2) dry powder blend:
In the slurry tank of planet-shaped blender, add LiFePO4 and inorganic conductive agent, stir then, get 10-20 sample the LiFePO4 that in slurry tank, is mixing in the whipping process and the inorganic conductive agent at random, test the powder resistance value of each sample then respectively, each sample powder resistance value deviation is less than 5%, then determine to stir, obtain powder mixture;
3) substep pulp preparation process:
According to (5-10): 100 mass ratio is dissolved into Kynoar in the N-methyl pyrrolidone, obtains the PVDF colloidal fluid; The PVDF colloidal fluid is divided into four parts; In powder mixture, add first part of PVDF colloidal fluid, stir, obtain mixed slurry A; Continue to add second part PVDF colloidal fluid then in the mixed slurry A, stir, obtain mixed slurry B; Adding the 3rd part of PVDF colloidal fluid again in the mixed slurry B stirs, and in whipping process, paddle and slurry tank are carried out scraper so that no solid dry powder exists among the mixed slurry C that guarantees to obtain, open vacuum then, mixed slurry C is carried out vacuum stirring remove bubble among the mixed slurry C; Add the 4th part of PVDF colloidal fluid in the process mixed slurry C of vacuum stirring, vacuum stirring is even then, obtains mixed slurry;
4) add the N-methyl pyrrolidone in mixed slurry, vacuum stirring is even, and the viscosity that obtains is at the lithium ion anode slurry of 3000-5000cps.
Described step 2) be that the revolution speed with 5rpm, the mixing speed of 10rpm are done mixed in.
Described step 3) is divided in four parts the PVDF colloidal fluid, first part of PVDF colloidal fluid accounts for the 28-35% of PVDF colloidal fluid gross mass, second part of PVDF colloidal fluid accounts for the 12-18% of PVDF colloidal fluid gross mass, the 3rd part of PVDF colloidal fluid accounts for the 25-30% of PVDF colloidal fluid gross mass, and the 4th part of PVDF colloidal fluid accounts for the 20-30% of PVDF colloidal fluid gross mass.
Described step 3) is that the mixing speed of revolution speed, 20-35rpm with 10-20rpm stirs and obtains mixed slurry A's when adding first part of PVDF colloidal fluid, being that the mixing speed of revolution speed, 30-45rpm with 20-30rpm stirs and obtains mixed slurry B when adding second part of PVDF colloidal fluid, is that the mixing speed of revolution speed, 50-70rpm with 30-45rpm stirs and obtains mixed slurry C's when adding the 3rd part of PVDF colloidal fluid; To being that the revolution speed with 40-60rpm, the mixing speed vacuum stirring of 60-90rpm evenly obtain mixed slurry when adding the 4th part of PVDF colloidal fluid among the mixed slurry C of vacuum stirring; Step 4) is even with 10-20rpm revolution speed, 20-35rpm mixing speed vacuum stirring.
Described step 2)-3 the temperature) is all controlled at 20 ℃-40 ℃, the vacuum degree of vacuum stirring in step 3) and the step 4) 〉-0.06MPa.
Use the sand net filtration during described lithium ion anode slurry discharging.
A kind of to adopt the viscosity of the lithium ion anode slurry of this method preparation be 3000-5000cps, and the lithium ion anode slurry comprises that N-methyl pyrrolidone and mass ratio are (85-95): (3-8): LiFePO4 (2-10), Kynoar and inorganic conductive agent.
The median particle diameter of described LiFePO4 is 5-15um, and specific area is 0.2-0.4; The molecular weight of Kynoar is at 500000-900000.
Described inorganic conductive agent is made up of Super-P material and the KS-6 of arbitrary proportion.
The median particle diameter of described Super-P material is 0.2-0.6um, and specific area is 30-50; The median particle diameter of KS-6 is 2-9um, and specific area is 0.8-1.6.
Further, described step 3) is carried out scraper so that the powder mixture that obtains mixes to paddle and slurry tank in the process that stirs;
Add first part of PVDF colloidal fluid in the described step 4) mixture, in the process that stirs paddle and slurry tank carried out scraper so that the mixed slurry A that obtains does not have solid dry powder exists; Continue to add second part PVDF colloidal fluid in the mixed slurry A, in the process that stirs paddle and slurry tank carried out scraper so that the mixed slurry B that obtains does not have solid dry powder exists; To through adding among the mixed slurry C of vacuum stirring in the 4th part of uniform process of PVDF colloidal fluid vacuum stirring paddle and slurry tank being carried out scraper so that the mixed slurry that obtains does not have solid dry powder exists.
Carry out scraper so that lithium ion anode slurry mix to paddle and slurry tank described the adding in the uniform process of N-methyl pyrrolidone vacuum stirring in the mixed slurry.
Compared with prior art, beneficial effect of the present invention is:
The degree that mixes of judging dry powder in the method for diverse location test powders resistance value that in the dry powder blend process, adopts of the present invention, make the inorganic conductive agent in LiFePO4, be uniformly dispersed, solved the defective that conductive agent is reunited easily in the lithium ion anode slurry that makes.In addition, the PVDF colloidal fluid is that branch four times adds in substep pulp preparation process, has broken through that the art is mixed solid material earlier in slurrying material process and the conventional thought of the disposable adding of glue, has obtained good effects on slurry making.In addition, utilize the lithium ion anode slurry good uniformity of method of the present invention preparation, the electrode slice resistance made is low, sedimentation is little, slurry viscosity changes little.
Further, temperature in PVDF colloidal fluid process for preparation, dry powder blend stage and substep pulp preparation stage of the present invention is all controlled at 20 ℃-40 ℃, can guarantee lithium ion anode slurry LiFePO4 stable existence in preparation process like this, oxidation does not take place.
Further, the present invention all carries out scraper to paddle and slurry tank in dry powder blend and substep pulp preparation process makes that no solid dry powder exists in the slurry that obtains, and has further guaranteed the uniformity of mixing.
Embodiment
Be described in further details below in conjunction with the present invention of embodiment.
Embodiment 1:
1) mass ratio by 90:7:2:1 takes by weighing LiFePO4, Kynoar, Super-P material and KS-6 respectively;
2) dry powder blend:
The slurry tank of planet-shaped blender is cleaned up and dries up, add LiFePO4, Super-P material and KS-6, do with revolution speed, the 10rpm mixing speed of 5rpm then and mix 30min, keep whipping temp at 20-40 ℃ in the whipping process, and according to circumstances paddle and slurry tank are needed in good time scraper, so that the powder mixture that obtains mixes; 10 samples of all directions grab sample the LiFePO4 that in slurry tank, is mixing in the whipping process, Super-P material and KS-6 and the inorganic conductive agent, test the powder resistance value of these 10 samples respectively, each sample powder resistance value deviation is less than 5%, be considered as stirring this moment, obtains powder mixture;
3) substep pulp preparation process:
Mass ratio according to 8:100 is dissolved into Kynoar in the N-methyl pyrrolidone under 20-40 ℃, obtains the PVDF colloidal fluid; The PVDF colloidal fluid is divided into four parts, and first part of PVDF colloidal fluid accounts for 28% of PVDF colloidal fluid gross mass, 30% 4th part of PVDF colloidal fluid that 12%, the three part of PVDF colloidal fluid that second part of PVDF colloidal fluid accounts for PVDF colloidal fluid gross mass accounts for PVDF colloidal fluid gross mass accounts for 30% of PVDF colloidal fluid gross mass;
In powder mixture, add first part of PVDF colloidal fluid, under 20-40 ℃, make evenly with the revolution speed of 10rpm, the mixing speed stirring 20min of 20rpm then, obtain mixed slurry A; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry A that obtains no dry powder exist;
Continue to add second part PVDF colloidal fluid in the mixed slurry A, under 20-40 ℃, stir 40min with the mixing speed of the revolution speed of 20rpm, 30rpm then and make evenly, obtain mixed slurry B; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry B that obtains no dry powder exist; Temperature in the PVDF colloidal fluid whipping process that continues second part of adding in mixed slurry A remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
In mixed slurry B, add the 3rd part of PVDF colloidal fluid, under 20-40 ℃, make evenly with the revolution speed of 30rpm, the mixing speed stirring 20min of 50rpm then, obtain mixed slurry C; Wherein, according to circumstances paddle and the in good time scraper of slurry tank are existed with no solid dry powder among the mixed slurry C that guarantees to obtain in the whipping process, open vacuum then ,-vacuum degree of 0.06MPa under bubble among the vacuum stirring removal mixed slurry C; Temperature in the PVDF colloidal fluid whipping process of the 3rd part of adding in mixed slurry B remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
To through adding the 4th part of PVDF colloidal fluid among the mixed slurry C of vacuum stirring, then under 20-40 ℃ with the mixing speed of the revolution speed of 40rpm, 60rpm with-the vacuum degree vacuum stirring 30min of 0.06MPa makes evenly, obtains mixed slurry; Wherein, in whipping process paddle and slurry tank being carried out scraper exists with no solid dry powder in the mixed slurry that guarantees to obtain; Temperature in the PVDF colloidal fluid vacuum stirring process of the 4th part of adding in the mixed slurry C of vacuum stirring remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
4) in mixed slurry, add the N-methyl pyrrolidone, then under 20-40 ℃ with the mixing speed of the revolution speed of 10rpm, 20rpm with-the vacuum degree vacuum stirring 10min of 0.06MPa, the viscosity of testing size is between 3000-5000cps, namely make the lithium ion anode slurry, when the discharging of lithium ion anode slurry, slurry need be used the sand net filtration, to eliminate the bulky grain in the slurry.
The viscosity of the lithium ion anode slurry of present embodiment preparation is 3000-5000cps, and the lithium ion anode slurry comprises that N-methyl pyrrolidone and mass ratio are LiFePO4, Kynoar, Super-P material and the KS-6 of 90:7:2:1.
Embodiment 2
Step 1) is to step 2) with the embodiment step 1) to step 2) identical;
3) substep pulp preparation process:
Mass ratio according to 8:100 is dissolved into Kynoar in the N-methyl pyrrolidone under 20-40 ℃, obtains the PVDF colloidal fluid; The PVDF colloidal fluid is divided into four parts, and first part of PVDF colloidal fluid accounts for 32% of PVDF colloidal fluid gross mass, 28% 4th part of PVDF colloidal fluid that 15%, the three part of PVDF colloidal fluid that second part of PVDF colloidal fluid accounts for PVDF colloidal fluid gross mass accounts for PVDF colloidal fluid gross mass accounts for 25% of PVDF colloidal fluid gross mass;
Add first part of PVDF colloidal fluid in the powder mixture, under 20-40 ℃, stir 30min with the mixing speed of the revolution speed of 15rpm, 28rpm then and make evenly, obtain mixed slurry A; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry A that obtains no dry powder exist;
Continue to add second part PVDF colloidal fluid in the mixed slurry A, then under 20-40 ℃ with 25rpm revolution speed, 38 rpm mixing speed stir 50min and make evenly, obtain mixed slurry B; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry B that obtains no dry powder exist; Temperature in the PVDF colloidal fluid whipping process that continues second part of adding in mixed slurry A remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
Add the 3rd part of PVDF colloidal fluid in the mixed slurry B, under 20-40 ℃, stir 30min with the mixing speed of the revolution speed of 35rpm, 55rpm then and make evenly, obtain mixed slurry C; Wherein, according to circumstances paddle and the in good time scraper of slurry tank are existed with no solid dry powder among the mixed slurry C that guarantees to obtain in the whipping process, open vacuum then ,-vacuum degree of 0.06MPa under bubble among the vacuum stirring removal mixed slurry C; Temperature in the PVDF colloidal fluid whipping process of the 3rd part of adding in mixed slurry B remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
To through adding the 4th part of PVDF colloidal fluid among the mixed slurry C of vacuum stirring, then under 20-40 ℃ with 50rpm revolution speed, 70rpm mixing speed with-the vacuum degree vacuum stirring 50min of 0.06MPa makes evenly, obtains mixed slurry; Wherein, in whipping process paddle and slurry tank being carried out scraper exists with no solid dry powder in the mixed slurry that guarantees to obtain; Temperature in the PVDF colloidal fluid vacuum stirring process of the 4th part of adding in the mixed slurry C of vacuum stirring remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
Step 4) is identical with step 4) among the embodiment 1.
The lithium ion anode slurry of present embodiment preparation is with embodiment 1.
Embodiment 3:
Step 1) is to step 2) with the embodiment step 1) to step 2) identical;
3) substep pulp preparation process:
Mass ratio according to 8:100 is dissolved into Kynoar in the N-methyl pyrrolidone under 20-40 ℃, obtains the PVDF colloidal fluid; The PVDF colloidal fluid is divided into four parts, and first part of PVDF colloidal fluid accounts for 35% of PVDF colloidal fluid gross mass, 30% 4th part of PVDF colloidal fluid that 18%, the three part of PVDF colloidal fluid that second part of PVDF colloidal fluid accounts for PVDF colloidal fluid gross mass accounts for PVDF colloidal fluid gross mass accounts for 17% of PVDF colloidal fluid gross mass;
Add first part of PVDF colloidal fluid in the powder mixture, under 20-40 ℃, stir 40min with the mixing speed of the revolution speed of 20rpm, 35rpm then and make evenly, obtain mixed slurry A; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry A that obtains no dry powder exist;
Continue to add second part PVDF colloidal fluid in the mixed slurry A, under 20-40 ℃, stir 60min with the mixing speed of the revolution speed of 30rpm, 45rpm then and make evenly, obtain mixed slurry B; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry B that obtains no dry powder exist; Temperature in the PVDF colloidal fluid whipping process that continues second part of adding in mixed slurry A remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
Add the 3rd part of PVDF colloidal fluid in the mixed slurry B, under 20-40 ℃, stir 40min with the mixing speed of the revolution speed of 45rpm, 70rpm then and make evenly, obtain mixed slurry C; Wherein, according to circumstances paddle and the in good time scraper of slurry tank are existed with no solid dry powder among the mixed slurry C that guarantees to obtain in the whipping process, open vacuum then ,-vacuum degree of 0.06MPa under bubble among the vacuum stirring removal mixed slurry C; Temperature in the PVDF colloidal fluid whipping process of the 3rd part of adding in mixed slurry B remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
To through adding the 4th part of PVDF colloidal fluid among the mixed slurry C of vacuum stirring, then under 20-40 ℃ with 60rpm revolution speed, 90rpm mixing speed with-the vacuum degree vacuum stirring 60min of 0.06MPa makes evenly, obtains mixed slurry; Wherein, in whipping process paddle and slurry tank being carried out scraper exists with no solid dry powder in the mixed slurry that guarantees to obtain; Temperature in the PVDF colloidal fluid vacuum stirring process of the 4th part of adding in the mixed slurry C of vacuum stirring remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
Step 4) is identical with step 4) among the embodiment 1.
The lithium ion anode slurry of present embodiment preparation is with embodiment 1.
The present invention gives Comparative Examples:
1) mass ratio by 90:7:2:1 takes by weighing LiFePO4, Kynoar, Super-P material and KS-6 respectively;
2) PVDF colloidal fluid preparation:
Mass ratio according to 8:100 is dissolved into Kynoar in the N-methyl pyrrolidone under 20-40 ℃, obtains the PVDF colloidal fluid;
3) LiFePO4, Super-P material and KS-6 are mixed, disperseed 1.5 hours, add the remaining NMP of prescription usually according to the design solid content then, disperseed 1 hour, add the PVDF colloidal fluid at last and disperse to become in 2 hours the lithium ion anode slurry.
The lithium ion anode slurry of present embodiment preparation is with embodiment 1.
Use coating machine to be uniformly coated on the 15um thick aluminum foil in the lithium ion anode slurry of embodiment 1-3 and the final preparation of Comparative Examples, dry stand-by.
Table 1 lithium ion anode slurry and make each index contrast behind the electrode slice
Annotate: after slurry configures, generally in 12 hours, can coating use, so contrast 12 hours indexs.
As shown in Table 1, the lithium ion anode slurry vacuum placement for preparing by the inventive method did not have sedimentation after 12 hours, and viscosity changes little, and the average resistance of the electrode slice that is made into is lower.And after 12 hours sedimentation is arranged by the slurry vacuum placement that this area conventional method is made, and viscosity changes greatly, and the average resistance of the electrode slice that is made into is higher.
Embodiment 4:
1) mass ratio by 85:8:3:4 takes by weighing LiFePO4, Kynoar, Super-P material and KS-6 respectively;
2) dry powder blend:
The slurry tank of planet-shaped blender is cleaned up and dries up, add LiFePO4, Super-P material and KS-6, do with revolution speed, the 10rpm mixing speed of 5rpm then and mix 30min, keep whipping temp at 20-40 ℃ in the whipping process, and according to circumstances paddle and slurry tank are needed in good time scraper, so that the powder mixture that obtains mixes; 16 samples of all directions grab sample the LiFePO4 that in slurry tank, is mixing in the whipping process, Super-P material and KS-6 and the inorganic conductive agent, test the powder resistance value of these 16 samples respectively, each sample powder resistance value deviation is less than 5%, be considered as stirring this moment, obtains powder mixture;
3) substep pulp preparation process:
Mass ratio according to 5:100 is dissolved into Kynoar in the N-methyl pyrrolidone under 20-40 ℃, obtains the PVDF colloidal fluid; The PVDF colloidal fluid is divided into four parts, and first part of PVDF colloidal fluid accounts for 35% of PVDF colloidal fluid gross mass, 25% 4th part of PVDF colloidal fluid that 18%, the three part of PVDF colloidal fluid that second part of PVDF colloidal fluid accounts for PVDF colloidal fluid gross mass accounts for PVDF colloidal fluid gross mass accounts for 22% of PVDF colloidal fluid gross mass;
In powder mixture, add first part of PVDF colloidal fluid, under 20-40 ℃, make evenly with the revolution speed of 10rpm, the mixing speed stirring 20min of 20rpm then, obtain mixed slurry A; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry A that obtains no dry powder exist;
Continue to add second part PVDF colloidal fluid in the mixed slurry A, under 20-40 ℃, stir 40min with the mixing speed of the revolution speed of 20rpm, 30rpm then and make evenly, obtain mixed slurry B; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry B that obtains no dry powder exist; Temperature in the PVDF colloidal fluid whipping process that continues second part of adding in mixed slurry A remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
In mixed slurry B, add the 3rd part of PVDF colloidal fluid, under 20-40 ℃, make evenly with the revolution speed of 30rpm, the mixing speed stirring 20min of 50rpm then, obtain mixed slurry C; Wherein, according to circumstances paddle and the in good time scraper of slurry tank are existed with no solid dry powder among the mixed slurry C that guarantees to obtain in the whipping process, open vacuum then ,-vacuum degree of 0.06MPa under bubble among the vacuum stirring removal mixed slurry C; Temperature in the PVDF colloidal fluid whipping process of the 3rd part of adding in mixed slurry B remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
To through adding the 4th part of PVDF colloidal fluid among the mixed slurry C of vacuum stirring, then under 20-40 ℃ with the mixing speed of the revolution speed of 40rpm, 60rpm with-the vacuum degree vacuum stirring 30min of 0.06MPa makes evenly, obtains mixed slurry; Wherein, in whipping process paddle and slurry tank being carried out scraper exists with no solid dry powder in the mixed slurry that guarantees to obtain; Temperature in the PVDF colloidal fluid vacuum stirring process of the 4th part of adding in the mixed slurry C of vacuum stirring remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
4) in mixed slurry, add the N-methyl pyrrolidone, then under 20-40 ℃ with the mixing speed of the revolution speed of 20rpm, 28rpm with-the vacuum degree vacuum stirring 15min of 0.06MPa, the viscosity of testing size is between 3000-5000cps, namely make the lithium ion anode slurry, when the discharging of lithium ion anode slurry, slurry need be used the sand net filtration, to eliminate the bulky grain in the slurry.
The viscosity of the lithium ion anode slurry of present embodiment preparation is 3000-5000cps, and the lithium ion anode slurry comprises that N-methyl pyrrolidone and mass ratio are LiFePO4, Kynoar, Super-P material and the KS-6 of 85:8:3:4.
Embodiment 5:
1) mass ratio by 95:3:1:1 takes by weighing LiFePO4, Kynoar, Super-P material and KS-6 respectively;
2) dry powder blend:
The slurry tank of planet-shaped blender is cleaned up and dries up, add LiFePO4, Super-P material and KS-6, do with revolution speed, the 10rpm mixing speed of 5rpm then and mix 30min, keep whipping temp at 20-40 ℃ in the whipping process, and according to circumstances paddle and slurry tank are needed in good time scraper, so that the powder mixture that obtains mixes; 20 samples of all directions grab sample the LiFePO4 that in slurry tank, is mixing in the whipping process, Super-P material and KS-6 and the inorganic conductive agent, test the powder resistance value of these 20 samples respectively, each sample powder resistance value deviation is less than 5%, be considered as stirring this moment, obtains powder mixture;
4) substep pulp preparation process:
Mass ratio according to 10:100 is dissolved into Kynoar in the N-methyl pyrrolidone under 20-40 ℃, obtains the PVDF colloidal fluid; The PVDF colloidal fluid is divided into four parts, and first part of PVDF colloidal fluid accounts for 35% of PVDF colloidal fluid gross mass, 30% 4th part of PVDF colloidal fluid that 15%, the three part of PVDF colloidal fluid that second part of PVDF colloidal fluid accounts for PVDF colloidal fluid gross mass accounts for PVDF colloidal fluid gross mass accounts for 20% of PVDF colloidal fluid gross mass;
In powder mixture, add first part of PVDF colloidal fluid, under 20-40 ℃, make evenly with the revolution speed of 10rpm, the mixing speed stirring 20min of 20rpm then, obtain mixed slurry A; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry A that obtains no dry powder exist;
Continue to add second part PVDF colloidal fluid in the mixed slurry A, under 20-40 ℃, stir 40min with the mixing speed of the revolution speed of 20rpm, 30rpm then and make evenly, obtain mixed slurry B; Wherein, in the whipping process according to circumstances to paddle and the in good time scraper of slurry tank so that among the mixed slurry B that obtains no dry powder exist; Temperature in the PVDF colloidal fluid whipping process that continues second part of adding in mixed slurry A remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
In mixed slurry B, add the 3rd part of PVDF colloidal fluid, under 20-40 ℃, make evenly with the revolution speed of 30rpm, the mixing speed stirring 20min of 50rpm then, obtain mixed slurry C; Wherein, according to circumstances paddle and the in good time scraper of slurry tank are existed with no solid dry powder among the mixed slurry C that guarantees to obtain in the whipping process, open vacuum then ,-vacuum degree of 0.06MPa under bubble among the vacuum stirring removal mixed slurry C; Temperature in the PVDF colloidal fluid whipping process of the 3rd part of adding in mixed slurry B remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
To through adding the 4th part of PVDF colloidal fluid among the mixed slurry C of vacuum stirring, then under 20-40 ℃ with the mixing speed of the revolution speed of 40rpm, 60rpm with-the vacuum degree vacuum stirring 30min of 0.06MPa makes evenly, obtains mixed slurry; Wherein, in whipping process paddle and slurry tank being carried out scraper exists with no solid dry powder in the mixed slurry that guarantees to obtain; Temperature in the PVDF colloidal fluid vacuum stirring process of the 4th part of adding in the mixed slurry C of vacuum stirring remains on 20-40 ℃ by the mode of logical 25 ℃ of cooling waters;
5) in mixed slurry, add the N-methyl pyrrolidone, then under 20-40 ℃ with the mixing speed of the revolution speed of 16rpm, 35rpm with-the vacuum degree vacuum stirring 30min of 0.06MPa, the viscosity of testing size is between 3000-5000cps, namely make the lithium ion anode slurry, when the discharging of lithium ion anode slurry, slurry need be used the sand net filtration, to eliminate the bulky grain in the slurry.
The viscosity of the lithium ion anode slurry of present embodiment preparation is 3000-5000cps, and the lithium ion anode slurry comprises that N-methyl pyrrolidone and mass ratio are LiFePO4, Kynoar, Super-P material and the KS-6 of 95:3:1:1.
The median particle diameter of the LiFePO4 in above-described embodiment 1-5 and the Comparative Examples is 5-15um, and specific area is 0.2-0.4; The molecular weight of Kynoar is at 500000-900000; The median particle diameter of Super-P material is 0.2-0.6um, and specific area is 30-50; The median particle diameter of KS-6 is 2-9um, and specific area is 0.8-1.6.
In making the pulp of lithium ion battery process, the consumption proportion that comprises compositions such as active material, conductive agent, binding agent and solvent that those skilled in the art can adopt usually is all applicable to the present invention.Innovation of the present invention is adopted the method in diverse location test powders resistance value in slurry dry powder preparation process, judge the degree that mixes of dry powder.In addition, in the pulp preparation process, divide four addings with glue, and each time speed is all variant, broken through in the art, in slurrying material process, with the conventional thought of solid material mixing earlier and the disposable adding of glue, obtained good effects on slurry making.Utilize the slurry good uniformity of method of the present invention preparation, the electrode slice resistance made is low, sedimentation is little, slurry viscosity changes little.
Claims (10)
1. the preparation method of a lithium ion anode slurry is characterized in that, comprises the steps:
1) by (85-95): (3-8): mass ratio (2-10) takes by weighing LiFePO4, Kynoar and inorganic conductive agent respectively;
2) dry powder blend:
In the slurry tank of planet-shaped blender, add LiFePO4 and inorganic conductive agent, stir then, get 10-20 sample the LiFePO4 that in slurry tank, is mixing in the whipping process and the inorganic conductive agent at random, test the powder resistance value of each sample then respectively, each sample powder resistance value deviation is less than 5%, then determine to stir, obtain powder mixture;
3) substep pulp preparation process:
According to (5-10): 100 mass ratio is dissolved into Kynoar in the N-methyl pyrrolidone, obtains the PVDF colloidal fluid; The PVDF colloidal fluid is divided into four parts; In powder mixture, add first part of PVDF colloidal fluid, stir, obtain mixed slurry A; Continue to add second part PVDF colloidal fluid then in the mixed slurry A, stir, obtain mixed slurry B; Adding the 3rd part of PVDF colloidal fluid again in the mixed slurry B stirs, and in whipping process, paddle and slurry tank are carried out scraper so that no solid dry powder exists among the mixed slurry C that guarantees to obtain, open vacuum then, mixed slurry C is carried out vacuum stirring remove bubble among the mixed slurry C; Add the 4th part of PVDF colloidal fluid in the process mixed slurry C of vacuum stirring, vacuum stirring is even then, obtains mixed slurry;
4) add the N-methyl pyrrolidone in mixed slurry, vacuum stirring is even, and the viscosity that obtains is at the lithium ion anode slurry of 3000-5000cps.
2. the preparation method of lithium ion anode slurry according to claim 1 is characterized in that: be that the revolution speed with 5rpm, the mixing speed of 10rpm are done mixed described step 2).
3. the preparation method of lithium ion anode slurry according to claim 1, it is characterized in that: described step 3) is divided in four parts the PVDF colloidal fluid, first part of PVDF colloidal fluid accounts for the 28-35% of PVDF colloidal fluid gross mass, second part of PVDF colloidal fluid accounts for the 12-18% of PVDF colloidal fluid gross mass, the 3rd part of PVDF colloidal fluid accounts for the 25-30% of PVDF colloidal fluid gross mass, and the 4th part of PVDF colloidal fluid accounts for the 20-30% of PVDF colloidal fluid gross mass.
4. according to the preparation method of claim 1 or 3 described lithium ion anode slurries, it is characterized in that: described step 3) is that the mixing speed of revolution speed, 20-35rpm with 10-20rpm stirs and obtains mixed slurry A's when adding first part of PVDF colloidal fluid, being that the mixing speed of revolution speed, 30-45rpm with 20-30rpm stirs and obtains mixed slurry B when adding second part of PVDF colloidal fluid, is that the mixing speed of revolution speed, 50-70rpm with 30-45rpm stirs and obtains mixed slurry C's when adding the 3rd part of PVDF colloidal fluid; To being that the revolution speed with 40-60rpm, the mixing speed vacuum stirring of 60-90rpm evenly obtain mixed slurry when adding the 4th part of PVDF colloidal fluid among the mixed slurry C of vacuum stirring; Step 4) is even with 10-20rpm revolution speed, 20-35rpm mixing speed vacuum stirring.
5. the preparation method of lithium ion anode slurry according to claim 1 is characterized in that: described step 2)-3) in temperature all control at 20 ℃-40 ℃ the vacuum degree of vacuum stirring in step 3) and the step 4)-0.06MPa.
6. the preparation method of lithium ion anode slurry according to claim 1 is characterized in that: use the sand net filtration during described lithium ion anode slurry discharging.
7. the lithium ion anode slurry of the method preparation described in any one of claim 1-6, it is characterized in that: the viscosity of this lithium ion anode slurry is 3000-5000cps, and the lithium ion anode slurry comprises that N-methyl pyrrolidone and mass ratio are (85-95): (3-8): LiFePO4 (2-10), Kynoar and inorganic conductive agent.
8. lithium ion anode slurry according to claim 7, it is characterized in that: the median particle diameter of described LiFePO4 is 5-15um, specific area is 0.2-0.4; The molecular weight of Kynoar is at 500000-900000.
9. lithium ion anode slurry according to claim 7, it is characterized in that: described inorganic conductive agent is made up of Super-P material and the KS-6 of arbitrary proportion.
10. lithium ion anode slurry according to claim 9, it is characterized in that: the median particle diameter of described Super-P material is 0.2-0.6um, specific area is 30-50; The median particle diameter of KS-6 is 2-9um, and specific area is 0.8-1.6.
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