CN108232195B - Pole piece forming method of water-based ion battery based on polytetrafluoroethylene binder - Google Patents

Pole piece forming method of water-based ion battery based on polytetrafluoroethylene binder Download PDF

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CN108232195B
CN108232195B CN201611148240.1A CN201611148240A CN108232195B CN 108232195 B CN108232195 B CN 108232195B CN 201611148240 A CN201611148240 A CN 201611148240A CN 108232195 B CN108232195 B CN 108232195B
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pole piece
binder
slurry
ball milling
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CN108232195A (en
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曾诗蒙
刘宇
贺诗阳
张永献
贺健
夏骥
张娜
李录平
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Benan Energy Technology Shanghai Co ltd
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Shanghai Institute of Ceramics of CAS
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    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • 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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Abstract

The invention relates to a pole piece forming method of a water-based ion battery based on a polytetrafluoroethylene binder, which comprises the following steps: step 1) taking ceramic powder and an inorganic carbon source conductive agent used by a water-based ion battery electrode as raw materials, taking water as a solvent, adding polytetrafluoroethylene as a binder, and performing ball milling to obtain uniform slurry; step 2) filtering the obtained slurry to obtain a filter cake, and further drying the obtained filter cake to obtain dry powder; step 3) granulating and sieving the obtained dry powder to obtain granular powder with uniform granularity; and 4) preparing the battery pole pieces in batches by using the obtained granular powder by a dry pressing method. The invention adopts a mode of ball milling slurry preparation and combined granulation, the obtained powder is granular, the flowability problem of the powder caused by the binder is greatly improved, the pole piece forming is easy to control, and the method is suitable for preparing the thick pole piece by adopting dry pressing forming.

Description

Pole piece forming method of water-based ion battery based on polytetrafluoroethylene binder
Technical Field
The invention relates to a pole piece forming method based on Polytetrafluoroethylene (PTFE) binder as a water-based ion battery, in particular to a batch pole piece production process which adopts ball milling mixing, conventional drying granulation, and control by combining an automatic powder tabletting forming machine and an automatic weighing system, and belongs to the field of ceramic powder materials.
Background
Low cost power energy storage systems are currently being driven by new energy sources, and it is estimated that the worldwide annual market demand for storage batteries is around $ 150 billion, in terms of industrial storage batteries, such as: the device is used for UPS, power quality regulation, backup batteries and the like, and the total market amount can reach 50 hundred million dollars. In the united states, europe, and asia, a number of high performance battery enterprises are being built that produce energy for power system storage. In recent years, various new types of storage batteries have been successively developed and used in power systems. Regnesys Technologies (www.regenesys.com.au /) in the United kingdom is building a 15MW/120MW · h energy storage plant using PSB (polysufide Broe Flow Battery) cells with a net efficiency of about 75%. Lithium ion batteries are currently rapidly developing due to their high energy density and energy storage efficiency, and within recent years lithium batteries have already occupied 50% of the market share of small mobile device power supplies, but there is still some challenging task to do to produce large capacity lithium ion batteries, the main obstacle being their high cost, on the other hand due to the special packaging and the necessary internal overcharge protection circuitry required. The main advantages of aqueous ion batteries compared to other batteries are high energy storage efficiency (close to 100%) and long service life (3000 charges can be made per discharge no more than 80% of the stored energy). And is expected to be a storage battery with the lowest cost, which is also a storage battery harmless to the environment.
In the past, the electrolyte used in nickel-cadmium batteries, nickel-hydrogen batteries, super capacitors and the like is an organic system, the electrode preparation generally adopts a coating process, and in the coating process, a binder system has a great influence on the binding effect of an electrode material. The binder system is mainly used for increasing the binding strength of the electrode in the electrode and preventing the falling of active substances of the electrode in the cyclic charge and discharge process. The aqueous ion battery adopting the thick pole piece design has high difficulty in selecting the binder, and the binder must ensure the uniformity and safety of active substances during pulping and plays a role in binding active substance particles. Meanwhile, the electrolyte has good thermal stability and stability to electrolyte. Due to the adoption of the design of the thick pole piece, PTFE is selected as a binder, so that the pole piece powder has a series of advantages which are not possessed by other binders, for example, the pole piece powder has a fiber mesh structure, and has the characteristics of high porosity, high compressibility, excellent acid and alkali corrosion resistance, no aging, kneading and denaturation resistance, difficulty in powder falling, very high tensile strength and the like, but the realization of the industrial batch production of the pole piece has great challenge. The PTFE is used as a binder system of a water-based ion battery, 60% PTFE emulsion is commonly used as an electrode binder, and the difficulty lies in that irreversible coagulation is usually generated in the stirring and mixing process, so that the slurry has poor fluidity and poor mixing uniformity, and secondly, the problem of poor powder fluidity caused by the PTFE is difficult to solve, so that the production of a thick pole piece is difficult to adopt a dry pressing forming process, for example, CN102916186A discloses that a sodium ion battery cathode is prepared by uniformly mixing a cathode material, acetylene black and the binder PTFE and then performing rolling forming, the quality and the thickness of the pole piece are difficult to accurately control through rolling forming, the proportion of the anode and the cathode of the battery is difficult to control, the battery performance is greatly influenced, and the battery consistency is difficult to ensure. Therefore, the large-scale industrial production of the design of the thick battery pole piece by using PTFE as a water-based ion battery binder is reported in documents so far.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a pole piece forming method based on a polytetrafluoroethylene binder as a water-system ion battery, which has the advantages of short production period, low equipment cost, simple process, easy control and suitability for batch production.
The invention provides a method for forming a pole piece of an aqueous ion battery based on a Polytetrafluoroethylene (PTFE) binder, which comprises the following steps:
step 1) taking ceramic powder and an inorganic carbon source conductive agent used by a water-based ion battery electrode as raw materials, taking water as a solvent, adding polytetrafluoroethylene as a binder, and performing ball milling to obtain uniform slurry;
step 2) filtering the obtained slurry to obtain a filter cake, and further drying the obtained filter cake to obtain dry powder;
step 3) granulating and sieving the obtained dry powder to obtain granular powder with uniform granularity;
and 4) preparing the battery pole pieces in batches by using the obtained granular powder by a dry pressing method.
The invention adopts a mode of ball milling slurry preparation and combined granulation, the obtained powder is granular, the flowability problem of the powder caused by the binder is greatly improved, the pole piece forming is easy to control, and the method is suitable for preparing the thick pole piece by adopting dry pressing forming. The thickness of the pole piece obtained by the invention can be 0-3 mm.
In the present invention, the aqueous ion battery may be an aqueous sodium ion battery or an aqueous lithium ion battery.
In the invention, the pole piece can be a positive pole piece or a negative pole piece. Preferably, the ceramic powder of the positive pole piece is LiMn2O4、LiFePO4、LiCoO2、LiNiO2、λ-MnO2、NaMnO2At least one of (1). The ceramic powder of the negative pole piece is NaTi2(PO4)3、LiTi2(PO4)3At least one of (1).
Preferably, the conductive agent is an inorganic carbon source, preferably at least one of artificial graphite, natural graphite, activated carbon, graphene, carbon black, carbon fiber and mesoporous carbon.
Preferably, in the step 1), the content of the binder is 0 to 25 wt.%, preferably 5 to 20wt.% of the ceramic powder.
Preferably, in step 1), the solid content of the slurry obtained is 0 to 80 wt.%, preferably 10 to 60 wt.%.
Preferably, step 1) comprises:
pouring ceramic powder, a conductive agent, a solvent and ball milling beads into a ball milling barrel according to a certain proportion, and then carrying out ball milling for less than 5 hours at a rotating speed of 0-300 r/min to obtain first slurry, wherein zirconium oxide is used as the ball milling beads, and the ratio of the material to the balls is 1 (3-6); and adding a binder polytetrafluoroethylene into the obtained first slurry, and mixing and ball-milling at a rotating speed of 0-300 r/min for less than 5 hours. The problem of poor fluidity can be solved by adopting a step-by-step ball milling mode.
Preferably, in the step 2), the equipment used for filtering is a plate and frame filter press or a centrifugal filter equipment, filter cloth with pores of 0-100 μm, preferably 0-50 μm is selected, after dehydration to a certain humidity, solids on the filter cloth are obtained, and further dried by using an oven, preferably, the oven is set at a temperature of 80-150 ℃.
Preferably, in the step 3), a mechanical granulation mode is adopted, and a sieve with a mesh of 0-5 mm, preferably 0-3 mm is used for sieving. The prepared powder particles can increase the fluidity of the powder, the precision is easy to control in the pole piece forming process, and the dry pressing forming process is easy to adopt.
Preferably, in the step 4), an automatic powder tabletting and forming machine is adopted for tabletting. Preferably, an isometric method is used for tableting.
The key point of the invention is that the method is different from the traditional method for preparing the aqueous ion electrode pole piece by using the PTFE adhesive, the design of the thick pole piece is realized, the mode of ball-milling and slurry preparation combined granulation is adopted, the obtained powder is granular, the flowability problem of the powder caused by the adhesive is greatly improved, the pole piece forming is easy to control, and the quality error of the obtained pole piece can be controlled within 2 percent by combining with an accurate weighing system in the powder forming process. Compared with the prior art, the invention has the following advantages and beneficial effects:
1. through ball milling dispersion and addition of a binder PTFE, carbon coating of active materials such as graphite and the like can be realized, the porosity of a pole piece is improved, the specific surface is increased, the conductivity of the material is improved, and the electrochemical performance of the material is greatly improved;
2. through a mechanical granulation mode, particles with uniform size distribution can be obtained, the flowability of the powder is improved, and conditions are created for tabletting and forming of the powder;
3. powder automatic molding equipment combines accurate weighing system, can the quality of effectual control pole piece, guarantees the uniformity of pole piece, in addition, adopts dry pressing former can guarantee that pole piece pressure is adjustable, and thickness is controllable, and all aspects of parameter of pole piece porosity can all be adjusted. The pole piece forming yield is high, and the method is suitable for batch production;
4. the invention has the advantages of short production period, cheap equipment, simple process, easy control, obvious practical value and good application prospect.
Drawings
Fig. 1 is a flow chart of mass production of water-based ion battery pole pieces according to an example of the present invention;
FIG. 2 is an SEM image of powder particles obtained by granulation in example 1;
FIG. 3 is a pictorial representation of a batch produced ceramic pole piece of example 1, wherein the left side is the thickness of the test pole piece and the right side is the dimensions of the test pole piece;
fig. 4 is a charge-discharge curve diagram of a unit cell assembled by mass-produced pole pieces of example 1.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting. In addition, the lower limit value of the range value mentioned in the present invention is 0, and preferably 0 is not included.
The invention provides a method for forming a pole piece of a water-based ion battery based on a Polytetrafluoroethylene (PTFE) binder. In the present invention, an aqueous ion battery refers to an ion battery having an aqueous electrolyte, and examples thereof include an aqueous sodium ion battery and an aqueous lithium ion battery. The battery pole piece can be a positive pole piece or a negative pole piece. The invention is particularly suitable for preparing thick pole pieces, for example, the thickness of the pole pieces can be 0-3 mm.
The invention uses several specific raw materials to obtain slurry with certain viscosity and particle size by a step-by-step ball milling method. And further drying the slurry, and combining with a granulation process to obtain powder with uniform mixing and good fluidity, and batch-producing the pole pieces by a specific tabletting process. Fig. 1 is a flowchart of mass production of water-based ion battery electrode sheets according to an example of the present invention. The present invention is described below with reference to fig. 1.
Firstly, mixing materials to prepare slurry. Specifically, ceramic powder used for positive and negative electrodes of an aqueous ion battery, active material powder such as a conductive agent (e.g., a carbon source), and the like are used as raw material powder, water is used as a solvent, and Polytetrafluoroethylene (PTFE) as a binder is added thereto, and ball milling is performed to obtain uniform slurry.
The anode ceramic powder can adopt a material which is commonly used in the field and has a relatively high intercalation/deintercalation potential platform and in which sodium (or lithium) ions can be intercalated and deintercalated, such as LiMn2O4、LiFePO4、LiCoO2、LiNiO2、λ-MnO2、NaMnO2One or more of them. The cathode ceramic powder can be made of a material with a relatively low intercalation/deintercalation potential platform, such as NaTi, in which sodium (or lithium) ions can be intercalated and deintercalated2(PO4)3、LiTi2(PO4)3One or more of them. The purity of the raw material ceramic powder can be industrial grade, and can be synthesized by oneself or purchased commercially.
The carbon source can be an inorganic carbon source, preferably any one or more of artificial graphite, natural graphite, activated carbon, graphene, carbon black, carbon fiber and mesoporous carbon. The mass ratio of the ceramic powder to the conductive agent can be (50-95): (50-5).
The invention uses Polytetrafluoroethylene (PTFE) as a binder, which can enable the pole piece powder to have a fiber mesh structure, and has the characteristics of high porosity, high compressibility, excellent acid and alkali corrosion resistance, no aging, kneading denaturation resistance, difficult powder falling, high tensile strength and the like. The content of the binder may be 0 to 25 wt.%, preferably 5 to 20wt.% of the raw material powder (including the ceramic powder and the conductive agent). The porosity of the obtained pole piece can be adjusted by changing the using amount of the binder. For example, in the above range, as the amount of binder increases, the porosity of the pole piece also increases.
In ball milling, zirconia can be used as ball milling beads, and the material ball ratio can be 1 (3-6). The solid content of the obtained slurry is 0-80 wt.%, and preferably 10-60 wt.%. The viscosity of the slurry can be 0 to 1000 Pa.s.
In one example, a slurry with a certain viscosity and particle size is obtained by a step-and-ball milling method. Specifically, powder, a solvent and ball milling beads are poured into a ball milling barrel according to a certain proportion, and then ball milling is carried out for 0-5 hours at a rotating speed of 0-300 r/min to obtain first slurry; and adding a binder PTFE into the obtained first slurry, and mixing and ball-milling for 0-5 hours at a rotating speed of 0-300 r/min. Compared with one-step ball milling, the step-by-step ball milling can be carried out uniformly, and the PTFE binder is effectively dispersed.
Subsequently, the slurry is dried. Filtering the slurry to obtain a filter cake, reducing energy consumption for further drying the powder, and then drying the obtained filter cake in a further oven. The slurry contains a binder, and the pore space of the filter cloth can be controlled to control the filtration and dehydration of the slurry. Plate and frame filter press equipment or centrifugal filter equipment may be used. The pores of the filter cloth can be 0 to 100 μm. And after dehydration to a certain humidity, obtaining solid on the filter cloth, and further drying by using an oven to obtain dry powder. In the drying process, preferably, the set temperature of the drying oven is 80-150 ℃ (solvent volatilization temperature). The drying time may be 0 to 48 hours.
And (4) granulating the dried powder, and vibrating and sieving to obtain granular powder. Can be sieved by a 0-3 mm mesh. Therefore, powder particles with better fluidity can be obtained, and further pole piece molding is facilitated. Fig. 2 shows an SEM of the granulated powder in one example of the present invention, and it can be seen that the powder is granulated.
And further tabletting and molding the obtained granular powder to obtain the pole piece. In the invention, a dry pressing forming method can be adopted, and the positive and negative pole pieces of the battery can be automatically prepared in batches by a powder forming tablet press. Therefore, the thickness and the strength of the pole piece can be effectively controlled, and the pole pieces with uniform quality can be obtained in batches. During tabletting, a self-made specific die can be used, and the size required by production is met. The pressure of the bidirectional punch is adjusted to control the forming thickness and mechanical strength of the pole piece. The porosity of the pole piece can be adjusted by the using amount of the adhesive. For example, the pressure can be controlled to be 0 to 300 MPa. The thickness of the obtained pole piece can be 0-3 mm, and the strength of the pole piece can be 0-10 Mpa. The porosity of the pole piece can be adjusted within the range of 10-70%.
The invention has simple process, low cost, uniform ball milling and good powder dispersion degree. The humidity of the powder obtained by adopting a filter-pressing type or centrifugal drying mode is controllable, so that the energy consumption is reduced for further drying the powder, and the low-cost large-scale production preparation is facilitated. And the prepared powder adopts a step-by-step ball milling and combined granulation mode to solve the problem of poor flowability of the powder due to the binder, lays a foundation for batch production of the pole pieces, and also provides guarantee for the performance of the battery, so that the commercial application of the battery can be realized.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
60g of positive ceramic powder lambda-MnO2The method comprises the following steps of taking 10g of inorganic carbon source carbon black, 15g of activated carbon and 10g of natural graphite powder as raw materials, taking deionized water as a solvent, controlling the solid content of the powder to be 30 wt.%, taking zirconia as ball milling beads, and carrying out ball milling at a high speed of a coarse mill at a material-ball ratio of 1:5 for 2 hours at a speed of 120 revolutions per minute to obtain uniform slurry. Further 5 wt.% PTFE binder was added (different amounts of binder added had different effects on porosity, see table 1), and the slurry was decanted after further milling at 300 rpm for 5 hours. Filtering the obtained slurry by adopting a plate-and-frame filter pressing device to obtain a filter cake, further drying the obtained filter cake in a drying oven at a set temperature of 110 ℃, standing for 12 hours to obtain a dry blocky material, and feeding the obtained dry material into a drying ovenAnd (3) carrying out mechanical granulation, vibrating and sieving by using a 3mm mesh to obtain granular powder with uniform granularity, facilitating further pole piece forming, and further adopting a powder forming tablet press to automatically prepare the battery positive pole pieces in batches by using the obtained granular powder, wherein the pressure is 200 MPa.
Fig. 2 is an SEM image of the powder particles obtained by granulation in example 1, and it can be seen that the powder is granulated and has a uniform particle size. Fig. 3 is a diagram of a material object of the ceramic pole piece produced in batch in example 1, and it can be seen that the surface of the pole piece is smooth and flat, and the thickness consistency is good. The test shows that the thickness of the pole piece is 2.486mm, and the strength is 5.2 Mpa.
Table 1 shows the porosity of the electrode sheet obtained by changing the amount of the binder in example 1, which indicates that the influence of different amounts of the binder on the porosity is different;
TABLE 1 porosity of pole pieces corresponding to different PTFE contents
Figure BDA0001179300850000061
The batch-prepared pole pieces were assembled into a single cell for testing with reference to example 1, and the test results were: under the 0.1C multiplying power, the normal discharge capacity of the battery reaches 30Ah (see figure 4), and the performance requirement of the water system ion battery is met.
Example 2
70g of anode ceramic powder LiMn2O4The method comprises the following steps of taking an inorganic carbon source of 5g of carbon black, 5g of activated carbon and 10g of artificial graphite powder as raw materials, taking deionized water as a solvent, controlling the solid content of the powder to be 30 wt.%, taking zirconia as ball milling beads, and carrying out ball milling at a high speed of a coarse mill of 200 revolutions per minute for 4 hours to obtain uniform slurry, wherein the material-to-ball ratio is 1: 6. 10 wt.% of PTFE binder was added and the slurry was decanted after further ball milling at 250 rpm for 3 hours. Filtering the obtained slurry by adopting plate-and-frame filter pressing equipment to obtain a filter cake, further drying the obtained filter cake in a drying oven at a set temperature of 110 ℃, standing for 12 hours to obtain a dry blocky material, granulating the obtained dry material by using a swing granulator, and vibrating and sieving the dry material by using a 1mm mesh to obtain granular powder with uniform granularityThe obtained granular powder is further used for automatically preparing the battery positive pole piece in batches by adopting a powder forming tablet press, and the forming pressure is 300 MPa.
The test shows that the thickness of the pole piece is 2.512mm, the strength is 8.6Mpa, and the porosity is 35.86%.
Example 3
60g of negative electrode ceramic powder NaTi2(PO4)3The method comprises the steps of taking 10g of carbon black serving as an inorganic carbon source, 15g of natural graphite powder as a raw material, taking deionized water as a solvent, controlling the solid content of the powder to be 60wt.%, taking zirconium oxide as ball milling beads, wherein the material-ball ratio is 1:3, and carrying out ball milling for 5 hours at a high speed of 100 revolutions per minute by a coarse mill to obtain uniform slurry. 15 wt.% of PTFE binder was added and the slurry was decanted after further ball milling at 300 rpm for 2 h. Filtering the obtained slurry by adopting plate and frame type filter pressing equipment to obtain a filter cake, further drying the obtained filter cake in a drying oven, setting the temperature to be 110 ℃, standing for 12 hours to obtain a dry blocky material, mechanically granulating the obtained dry material, vibrating and sieving the dry material by using a 2mm mesh to obtain granular powder with uniform granularity, facilitating further pole piece forming, and further automatically preparing the battery negative pole pieces in batches by adopting a powder forming tablet press with the pressure of 300 MPa.
The test shows that the thickness of the pole piece is 2.623mm, the strength is 8.4Mpa, and the porosity is 40.5%.
Example 4
50g of negative electrode ceramic powder LiTi2(PO4)3The method comprises the following steps of taking 20g of inorganic carbon source carbon black, 10g of natural graphite powder as raw materials, taking deionized water as a solvent, controlling the solid content of the powder to be 50 wt.%, taking zirconia as ball milling beads, wherein the material-ball ratio is 1:5, and carrying out ball milling for 3 hours at a high speed of 150 revolutions per minute by a coarse mill to obtain uniform slurry. 20wt.% of PTFE binder was added and the slurry was decanted after further ball milling at 200 rpm for 3 hours. Filtering the obtained slurry by adopting plate-and-frame filter pressing equipment to obtain a filter cake, further drying the obtained filter cake in a drying oven at a set temperature of 100 ℃, standing for 24 hours to obtain a dry blocky material, mechanically granulating the obtained dry material, and vibrating by using a 2mm meshAnd (3) performing dynamic sieving to obtain granular powder with uniform granularity, facilitating further pole piece molding, and further automatically preparing the battery negative pole pieces in batches by adopting a powder molding tablet press with the molding pressure of 100 MPa.
The test shows that the thickness of the pole piece is 2.684mm, the strength is 4.5Mpa, and the porosity is 57.6%.
Industrial applicability: the method reduces the production difficulty and the production cost of the forming process of the pole piece of the water-system ion battery by using the PTFE adhesive, improves the electrochemical performance of the produced pole piece, and lays a foundation for the commercial production of the water-system ion battery.

Claims (7)

1. A thick pole piece forming method of a water system ion battery based on a polytetrafluoroethylene binder is characterized in that the water system ion battery is a water system sodium ion battery or a water system lithium ion battery, the pole piece forming method adopts a mode of ball milling slurry preparation and mechanical granulation, and comprises the following steps:
step 1) taking ceramic powder and an inorganic carbon source conductive agent used by a water-based ion battery electrode as raw materials, taking water as a solvent, adding polytetrafluoroethylene emulsion as a binder, and performing ball milling to obtain uniform slurry; the solid content of the obtained slurry is 10-60 wt.%; the content of the binder is 5-20 wt% of the ceramic powder;
step 2) filtering the obtained slurry to obtain a filter cake, and drying the obtained filter cake to obtain dry powder;
step 3) mechanically granulating the obtained dry powder, and sieving the powder by using a 1-5 mm mesh to obtain granular powder with uniform granularity;
step 4), carrying out dry pressing on the obtained granular powder, and tabletting by an isometric method to prepare battery pole pieces in batches;
the thickness of the battery pole piece is 0-3 mm, the strength is 4.5-10 Mpa, the porosity of the pole piece is adjustable within the range of 10-70%, and the quality error is controlled within 2%.
2. The method of claim 1, wherein the pole piece is a positive pole pieceOr a negative pole piece; the ceramic powder of the positive pole piece is LiMn2O4、LiFePO4、LiCoO2、LiNiO2、λ-MnO2、NaMnO2At least one of; the ceramic powder of the negative pole piece is NaTi2(PO4)3、LiTi2(PO4)3At least one of (1).
3. The method according to claim 1, wherein the conductive agent is at least one of artificial graphite, natural graphite, activated carbon, graphene, carbon black, carbon fiber, and mesoporous carbon.
4. The method of claim 1, wherein step 1) comprises: pouring ceramic powder, a conductive agent, a solvent and ball milling beads into a ball milling barrel according to a certain proportion, and then carrying out ball milling for less than 5 hours at a rotating speed of 150-300 r/min to obtain first slurry, wherein zirconium oxide is used as the ball milling beads, and the ratio of the material to the balls is 1 (3-6); and adding a binder polytetrafluoroethylene into the obtained first slurry, and mixing and ball-milling for less than 5 hours at a rotating speed of 200-300 r/min.
5. The method according to claim 1, wherein in the step 2), the equipment used for filtering is a plate-and-frame filter press or a centrifugal filter equipment, filter cloth with pores of 50-100 μm is selected, after the filter cloth is dehydrated to a certain humidity, solids on the filter cloth are obtained, and the obtained solid is further dried by using an oven.
6. The method according to claim 5, wherein the set temperature of the oven is 80-150 ℃.
7. The method as claimed in claim 1, wherein in step 4), the powder is tabletted by an automatic powder tabletting machine.
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