阅读说明：本技术 浆料电池的电极片及浆料电池 (Electrode plate of slurry battery and slurry battery ) 是由 陈永翀 孙晨宇 何颖源 王之英 谢晨 张艳萍 于 2018-06-26 设计创作，主要内容包括：本发明提供了一种浆料电池的电极片及浆料电池,该电极片包括多孔或网状的上表面集流体、下表面集流体以及层叠设置在所述上表面集流体和所述下表面集流体之间的电极层,所述电极层中含有电极活性导电颗粒；其中,所述上表面集流体和所述下表面集流体的周向上缝纫有用于将两者固定连接以阻挡电极层中的电极活性导电颗粒通过的缝纫线。本发明的电极片,通过缝纫的方式进行封边,有利于流水线化生产,简化了电极片的制作工艺、提高了电极片的密封安全性。(The invention provides an electrode plate of a slurry battery and the slurry battery, wherein the electrode plate comprises a porous or reticular upper surface current collector, a lower surface current collector and an electrode layer which is stacked between the upper surface current collector and the lower surface current collector, and the electrode layer contains electrode active conductive particles; and sewing threads for fixedly connecting the upper surface current collector and the lower surface current collector to block electrode active conductive particles in the electrode layer from passing through are sewn on the circumferential direction of the upper surface current collector and the lower surface current collector. The electrode plate disclosed by the invention is subjected to edge sealing in a sewing mode, so that the production line production is facilitated, the manufacturing process of the electrode plate is simplified, and the sealing safety of the electrode plate is improved.)

1. The electrode plate of the slurry battery is characterized by comprising a porous or reticular upper surface current collector, a lower surface current collector and an electrode layer which is stacked between the upper surface current collector and the lower surface current collector, wherein the electrode layer contains electrode active conductive particles; and sewing threads for fixedly connecting the upper surface current collector and the lower surface current collector to block electrode active conductive particles in the electrode layer from passing through are sewn on the circumferential direction of the upper surface current collector and the lower surface current collector.

2. The electrode sheet of claim 1, further comprising an elastic border for sewing together the upper and lower surface current collectors; the sewing thread penetrates through the upper surface current collector, the lower surface current collector and the elastic frame to be fixedly connected with the upper surface current collector and the lower surface current collector in a flat seam or an overlock mode.

3. The electrode sheet of claim 2, wherein the elastic frame is compression-sewn between the upper and lower surface current collectors; alternatively, the elastic frames are press-sewn in pairs and aligned with each other on the outer sides of the upper and lower surface current collectors.

4. The electrode sheet according to claim 2, wherein the elastic frame is made of porous foam, rubber, or flexible porous material, which is resistant to electrolyte; wherein the porous foam is one of polyolefin foam, conductive polyolefin foam and carbonized or non-carbonized melamine foam; the rubber is ethylene propylene rubber or fluorine rubber; the flexible porous material is polyester non-woven fabric or polypropylene non-woven fabric.

5. The electrode sheet according to claim 1, wherein the sewing thread is a conductive cable or a non-conductive cable, and the conductive cable is one or more of metal, metal with a conductive coating or an electronic conductive film coated on the surface, a composite material formed by twisting organic fibers and conductive fibers, and a composite material formed by winding conductive fibers on the surface of the organic fibers; the non-conductive cable is made of organic fibers, and the organic fibers are one or more of polyester fibers, nylon fibers, natural cotton and hemp, aramid fibers, polypropylene, polyethylene and fluorine fiber yarns.

6. The electrode sheet according to any one of claims 2 to 5, wherein when the electrode sheet is an electrode sheet of an infusion-type lithium slurry battery, the electrode layer is a coating body or powder having a predetermined thickness and size provided between the upper surface current collector and the lower surface current collector; the elastic frame is around the periphery of electrode layer and compress tightly the sewing and be in closed frame between upper surface mass flow body and the lower surface mass flow body.

7. The electrode tab according to claim 3, wherein when the electrode tab is an electrode tab of a slip-casting lithium slurry battery, the electrode layer is formed of slurry having fluidity; the elastic frame is a semi-closed frame, and the elastic frame and the upper surface current collector and the lower surface current collector jointly form an opening allowing the slurry to be injected.

8. The electrode sheet according to claim 1, wherein the upper surface current collector and the lower surface current collector are one or more of aluminum, aluminum alloy, stainless steel, silver, tin and titanium which are resistant to oxidation reaction when used in a positive electrode sheet; and when the upper surface current collector and the lower surface current collector are used for the negative plate, the upper surface current collector and the lower surface current collector are one or more of copper, stainless steel, nickel, titanium, tin-plated copper, nickel-plated copper and silver-plated copper which are resistant to reduction reaction.

9. The electrode sheet according to claim 1, further comprising a leakage-proof material disposed at the edges of the elastic frame, the upper surface current collector and the lower surface current collector to prevent leakage of the electrode material, wherein the leakage-proof material is one or more of hot-melt polyethylene, polypropylene, modified olefin adhesive, polyamide and polyimide insulating tape.

10. A paste battery, comprising a battery case and a battery cell disposed in the battery case, wherein the battery cell comprises a plurality of positive electrode sheets/separators/negative electrode sheets alternately stacked, and wherein the positive electrode sheets and the negative electrode sheets are the electrode sheets according to any one of claims 1 to 9.

Technical Field

The invention relates to the field of batteries, in particular to an electrode plate of a slurry battery and the slurry battery.

Background

The electrode plate of the slurry battery is internally provided with slurry electrode materials. The electrode material in the slurry state is a conductive slurry formed by suspending or precipitating conductive particles in an electrolyte according to a certain proportion. When the slurry battery is subjected to external impact or vibration, the conductive particles are not bonded and fixed, so that the slurry battery can move in the electrolyte to form a dynamic conductive network. The conductive particles may contain only a conductive agent, or may be composite particles of an active material and a conductive agent. Since the electrode tabs of the paste battery contain non-adhesively fixed conductive particles inside, the peripheries of the electrode tabs of the paste battery must be sealed to prevent the conductive particles from leaking outside.

At present, the edge of an electrode plate of a slurry battery is generally sealed by adopting hot melting, glue bonding, mechanical welding and other modes. The existing sealing mode has complex process, is not easy to disassemble when the battery is recycled and regenerated, and the sealing part is easy to damage or crack after being soaked in electrolyte for a long time, so that the reliability can not be ensured.

Disclosure of Invention

The invention aims to provide an electrode plate of a slurry battery, which is subjected to edge sealing in a sewing mode so as to simplify the manufacturing process of the electrode plate and facilitate the production of a production line.

According to an aspect of the present invention, there is provided an electrode sheet for a slurry battery, the electrode sheet including a porous or mesh-shaped upper surface current collector, a lower surface current collector, and an electrode layer stacked between the upper and lower surface current collectors. The electrode layer contains electrode active conductive particles, and sewing threads for fixedly connecting the upper surface current collector and the lower surface current collector so as to block the electrode active conductive particles in the electrode layer from passing through are sewn on the circumferential direction of the upper surface current collector and the lower surface current collector.

The electrode active conductive particles may be positive electrode active conductive particles, or may be negative electrode lithium-embeddable conductive particles. The non-adhesively secured positive electrode active conductive particles and/or the non-adhesively secured negative electrode intercalatable lithium conductive particles are capable of moving in the electrolyte to form a positive electrode slurry and/or a negative electrode slurry, respectively. The mass ratio of the positive electrode active conductive particles to the positive electrode slurry may be 10% to 90%, preferably 15% to 80%, and the mass ratio of the negative electrode lithium embeddable conductive particles to the negative electrode slurry may be 10% to 90%, preferably 15% to 80%. The average particle size of the positive active conductive particles can be 0.05-500 mu m, and the mass ratio of the positive active material to the conductive agent can be 20-98: 80-2; the average particle size of the negative electrode lithium-embeddable conductive particles can be 0.05-500 mu m, and the mass ratio of the negative electrode lithium-embeddable material to the conductive agent can be 20-98: 80-2.

Therefore, after the upper surface current collector and the lower surface current collector are sewn by the sewing thread, the positive active conductive particles in the positive slurry can be blocked, or the negative electrode in the negative slurry can be inserted with the lithium conductive particles to pass through, but the penetration of the electrolyte is not blocked. The positive electrode active conductive particles are a mixture of a positive electrode active material and a conductive agent, and the negative electrode lithium-embeddable conductive particles are a mixture of a negative electrode active material and a conductive agent.

The positive active material is one or a mixture of more of lithium-containing lithium iron phosphate, lithium manganese phosphate, doped lithium manganese oxide, lithium cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt oxide, lithium nickel manganese iron oxide and other lithium-containing metal oxides.

The negative active material is metallic lithium, or one or a mixture of more of aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide and carbon material which can be reversibly intercalated with lithium.

The conductive agent is one or a mixture of more of carbon black, carbon fiber, Ketjen black, graphene and metal particles.

Preferably, the electrode sheet further comprises an elastic frame for sewing together the upper surface current collector and the lower surface current collector. The sewing thread is inserted into the upper surface current collector, the lower surface current collector and the elastic frame to fixedly connect the upper surface current collector and the lower surface current collector in a flat seam or an overlock manner. In order to enable ions in the electrolyte to migrate between the positive and negative electrode layers, the upper surface current collector and the lower surface current collector are preferably porous foils or mesh-shaped current collectors. When the electrode plate is prepared, the current collectors on the upper surface and the lower surface can be closely sewed together along the edge of the electrode material around the circumference so as to prevent the leakage of electrode active conductive particles and prevent the permeation of electrolyte. The electrode plate disclosed by the invention is subjected to edge sealing in a sewing mode, the process is simple, the sewing thread cannot be damaged after being soaked in the electrolyte for a long time, and the sealing reliability is ensured.

By combining the sewing thread and the elastic frame, on one hand, the sealing property of the electrode plate can be improved; on the other hand, the current collector can be protected from being damaged by the traction of the sewing thread. Wherein the sewing track is one or more of a straight line, a broken line or a curve. When the cross section of the electrode sheet is rectangular, the sewing pattern may be formed as a straight line or a wavy line along four sides of the rectangle.

Preferably, the elastic frame is tightly pressed and sewn between the upper surface current collector and the lower surface current collector; or, the elastic frames are paired and aligned with each other to press and sew the outer sides of the upper and lower surface current collectors.

The current collectors on the upper surface and the lower surface can be in a rectangular structure, and the elastic frame can be in a rectangular closed strip-shaped structure or a rectangular semi-closed strip-shaped structure with an opening. The elastic frame has a certain width. Thus, the elastic frame can be vertically aligned with the current collectors on the upper surface and the lower surface and is closely sewed together. When the elastic frame is tightly pressed and sewn between the upper surface current collector and the lower surface current collector, a cavity for accommodating an electrode material can be formed among the upper surface current collector, the lower surface current collector and the elastic frame. When the elastic frames are paired and pressed tightly outside the upper and lower surface current collectors in alignment with each other, a cavity for accommodating an electrode material can be formed between the upper and lower surface current collectors.

Preferably, the elastic frame is made of electrolyte-resistant porous foam or rubber, or the elastic frame is made of electrolyte-resistant flexible porous material by rolling. The porous foam is polyolefin foam, carbonized or non-carbonized melamine foam or conductive polyolefin foam, etc. The rubber is ethylene propylene rubber or fluorine rubber. The flexible porous material is polyester non-woven fabric or polypropylene non-woven fabric. Therefore, the elastic frame is beneficial to the electrolyte to infiltrate and soak the pole piece from the side edge.

Preferably, the sewing thread is a conductive cable or a non-conductive cable, the conductive cable is one or more of metal, metal with a conductive coating attached to the surface or an electronic conductive film coated on the surface, a composite material formed by twisting organic fibers and conductive fibers and winding the conductive fibers on the surface of the organic fibers, and the like. The non-conductive cable is organic fiber, and the organic fiber is one or more of polyester fiber, nylon fiber, natural cotton and hemp, aramid fiber, polypropylene, polyethylene, fluorine fiber yarn and the like.

When the metal cable is used for the positive electrode sheet, it is required to be resistant to oxidation reaction, and a specific material may be one of aluminum, aluminum alloy, stainless steel, silver, tin, titanium, or the like, and preferably aluminum. When the metal cable is used for the negative electrode sheet, the metal cable is required to be resistant to reduction reaction, and the specific material may be one of copper, stainless steel, nickel, titanium, tin-plated copper, nickel-plated copper, silver-plated copper, and the like, and preferably is nickel-plated stainless steel. The conductive coating may be a conductive carbon material coating or a metal coating, preferably a conductive carbon material coating. The organic fiber comprises polyester fiber, nylon fiber, natural cotton and hemp, aramid fiber, polypropylene, polyethylene, fluorine fiber yarn and other organic fibers with good electrolyte resistance. The conductive fibers may be carbon fibers or conductive metal fibers, or the like. The electron conducting film may be a conductive carbon material coating or a metal coating.

Preferably, when the electrode sheet is an electrode sheet of an electrolyte injection type lithium slurry battery, the electrode layer is a coating body or powder with a predetermined thickness and size, which is arranged between the upper surface current collector and the lower surface current collector. The elastic frame is a closed frame which surrounds the periphery of the electrode layer and is tightly pressed and sewn between the upper surface current collector and the lower surface current collector. The thickness of the elastic frame is larger than that of the coating body or the powder.

Preferably, when the electrode tab is an electrode tab of a slip-casting lithium slurry battery, the electrode layer is formed of slurry having fluidity. The elastic frame is a semi-closed frame, and the elastic frame and the current collectors on the upper surface and the lower surface form an opening allowing slurry to be injected together. Therefore, the current collector and the elastic frame can be sewn together to form a semi-finished product, and then electrode slurry is injected into the semi-finished product to manufacture the electrode plate.

Preferably, when the current collector is used for the positive plate, the material of the current collector is one or more of aluminum, alloy aluminum, stainless steel, silver, tin, titanium and the like which are resistant to oxidation reaction; when the current collector is used for the negative plate, the material of the current collector is one or more of copper, stainless steel, nickel, titanium, tin-plated copper, nickel-plated copper, silver-plated copper and the like which are resistant to reduction reaction.

The current collector can be a metal net with meshes in a square shape, a diamond shape, a rectangular shape or a polygonal shape; or, a porous metal foam having a porous structure; or a metal plate (metal foil) that is mechanically stamped or chemically etched to allow ions to pass through or permeate. The current collector is preferably aluminum when used in the positive electrode; when the current collector is used for the negative electrode, nickel-plated stainless steel is preferable.

Preferably, the electrode plate further comprises a leakage-proof material arranged at the edges of the elastic frame and the current collectors on the upper and lower surfaces to prevent the leakage of the electrode layer material, wherein the leakage-proof material is one or more of hot-melt polyethylene, polypropylene, modified olefin adhesive, polyamide and polyimide insulating tape. According to another aspect of the present invention, there is also provided a slurry battery, which includes a battery casing and a battery cell disposed in the battery casing, wherein the battery cell includes a plurality of positive electrode sheets/separators/negative electrode sheets alternately stacked, and the positive electrode sheets and the negative electrode sheets are the above-mentioned electrode sheets.

The invention has the advantages that: (1) the peripheral edge of the electrode plate of the slurry battery is sealed by adopting a sewing thread sewing method, so that the protection and sealing of the edge of the electrode plate can be completed at one time, and the production process is simplified. (2) The equipment investment cost required in the sewing process is low, the process is mature, and the method is favorable for the streamlined production. (3) The combination of sewing thread and elasticity frame can be sealed around the electrode piece better on the one hand, and on the other hand is favorable to it to be disassembled at the in-process of battery recovery regeneration.

Drawings

The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings. Wherein:

fig. 1 is a schematic structural view of an electrode tab of a slurry battery according to an embodiment of the present invention;

fig. 2 is a schematic structural view of an electrode tab of a slurry battery according to another embodiment of the present invention;

FIG. 3 is a cross-sectional view of FIG. 2;

fig. 4 is a schematic structural view of an electrode tab of the slip-casting type slurry battery of the present invention.

Description of reference numerals:

100-electrode plate of slurry battery, 101-upper surface current collector, 102-lower surface current collector, 103-electrode layer, 104-elastic frame, 105-sewing thread, 1041-opening.

In the drawings, like parts are provided with like reference numerals. The drawings are not to scale.

Detailed Description

The invention will be further explained by embodiments in conjunction with the drawings.

As shown in fig. 1 to 3, the present invention provides an electrode tab 100 of a paste battery. The electrode sheet 100 includes a porous or mesh-shaped upper surface current collector 101, a lower surface current collector 102, and an electrode layer 103 stacked between the upper and lower surface current collectors. The electrode layer contains electrode active conductive particles. Sewing threads 105 for fixedly connecting the upper and lower surface current collectors to block passage of electrode active conductive particles in the electrode layer 103 are sewn in the circumferential direction of the upper and lower surface current collectors.

In a specific embodiment of the present invention, when the electrode sheet 100 is a positive electrode sheet, the upper surface current collector 101 and the lower surface current collector 102 both use rectangular aluminum mesh or aluminum foil with holes, and when the electrode sheet 100 is a negative electrode sheet, the upper surface current collector 101 and the lower surface current collector 102 both use rectangular copper mesh or copper foil with holes.

The electrode layer 103 may be a positive electrode layer or a negative electrode layer. When the electrode layer is a positive electrode layer, it includes a positive active conductive material, which may be a mixture of lithium iron phosphate, ketjen black, and PVDF. When the electrode layer is a negative electrode layer, it includes a negative active conductive material, which may be a mixture of graphite, ketjen black, and PVDF.

The sewing thread 105 may be a nylon thread.

In order to protect the current collectors from being damaged by being pulled by the sewing threads, the electrode sheet further comprises an elastic frame 104 for sewing the upper and lower surface current collectors together. The sewing thread 105 is inserted through the upper and lower surface current collectors and the elastic frame 104 to sew the upper and lower surface current collectors flat (fig. 1) or to wrap the upper and lower surface current collectors (fig. 2 and 3). When the current collectors on the upper and lower surfaces are both rectangular structures, the elastic frame is a rectangular closed or semi-closed frame.

In addition, during sewing, the elastic frame 104 and the current collector are in a compression state. The elastic frame 104 is tightly pressed and sewn between the upper surface current collector and the lower surface current collector; or, the current collectors are tightly sewed outside the upper and lower surface current collectors in pairs and aligned with each other.

The electrode plate edge-sealed by adopting the sewing mode is preferably used for the lithium paste battery.

According to different preparation processes of lithium slurry batteries, the lithium slurry batteries can be divided into a liquid injection type and a slip casting type.

When the electrode tab is an electrode tab of an electrolyte-type lithium slurry battery, the electrode layer 103 is a coating body or powder having a predetermined thickness and size provided between the upper and lower surface current collectors. The elastic frame 104 is a closed frame which surrounds the periphery of the electrode layer 103 and is tightly sewn between the upper and lower surface current collectors. Specifically, the positive electrode active conductive material of the liquid-injection type battery is a mixture of lithium iron phosphate, ketjen black and PVDF in a mass ratio of 85:13: 2. The negative electrode active conductive material is a mixture of graphite, ketjen black and PVDF in a mass ratio of 90:5: 5. The predetermined thickness of the coated body or powder (after compaction) is 0.5-1.5 mm.

When the electrode tab is an electrode tab of a slip-casting lithium paste battery, the electrode layer 103 is formed of a slurry having fluidity. The flexible bezel 104 is a semi-enclosed bezel. The elastic frame 104 and the upper and lower surface current collectors are jointly formed with openings 1041 for allowing slurry to be injected. Specifically, as shown in fig. 4, an opening 1041 is formed on the elastic frame 104. The positive electrode active conductive material is a mixture of lithium iron phosphate, Ketjen black and PVDF, wherein the mass ratio of the lithium iron phosphate to the Ketjen black is 85:13: 2. The negative electrode active conductive material is a mixture of graphite, ketjen black and PVDF in a mass ratio of 90:5: 5. Wherein, the preparation proportion of the anode active conductive material or the cathode active conductive material and the electrolyte is 10-60%.

The following examples 1 to 5 illustrate the production of positive and negative electrode sheets for liquid-injected lithium-slurry batteries and slip-cast lithium-slurry batteries.