CN115775883B - Surface modification method of lithium iron phosphate positive electrode material - Google Patents
Surface modification method of lithium iron phosphate positive electrode material Download PDFInfo
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- CN115775883B CN115775883B CN202310102390.2A CN202310102390A CN115775883B CN 115775883 B CN115775883 B CN 115775883B CN 202310102390 A CN202310102390 A CN 202310102390A CN 115775883 B CN115775883 B CN 115775883B
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Abstract
The invention discloses a surface modification method of a lithium iron phosphate positive electrode material, and relates to the technical field of modification of lithium iron phosphate positive electrode materials. Comprises the following steps of; step one: preparing a lithium iron phosphate foil; step two: placing a lithium iron phosphate foil roll into a lithium iron phosphate modification device; step three: cleaning the modified surface of the modified lithium iron phosphate foil, drying and then rewinding; in the second step, the lithium iron phosphate modification equipment comprises a frame, wherein a cover plate is fixedly connected to the top of the frame, and two spraying mechanisms are arranged on the top of the cover plate. According to the invention, two spraying mechanisms are used for spraying the medicament twice, the first spraying is a reducing sugar solution, the other is a newly configured silver ammonia solution, and a silver mirror can be generated on one side of the lithium iron phosphate foil by utilizing the reaction of the reducing sugar solution and the newly configured silver ammonia solution, so that a silver layer is attached to the surface of the lithium iron phosphate foil, the high conductivity of silver is utilized, the conductivity of the anode is improved, and the charge and discharge capacity and the low temperature resistance of a battery using the modified lithium iron phosphate foil as the anode are improved.
Description
Technical Field
The invention relates to the technical field of modification of lithium iron phosphate anode materials, in particular to a surface modification method of a lithium iron phosphate anode material.
Background
The cycle life of the lithium iron phosphate serving as a common positive electrode material of the lithium ion battery basically can reach more than 2000 times, even more than 3500 times, and some specific energy storage batteries can reach 4000-5000 times, and under certain conditions, the service life can reach 7-8 years.
The surface modification method of the lithium iron phosphate anode material comprises a plasma polymerization method for coating conductive polymers, surface fluorination, nitridation, vulcanization and the like, wherein the surface modification method comprises the steps of uniformly mixing lithium iron phosphate powder and conductive polymer monomers, placing the mixture in a discharge plasma reactor to coat the conductive polymers on the surface of the lithium iron phosphate or placing the lithium iron phosphate powder in the discharge plasma reactor, introducing working gas CF4, NH3, CS2 or H2S for ionization to generate F, N, S free radicals, and carrying out fluorination, nitridation and vulcanization treatment modification on the surface of the lithium iron phosphate material. The method has great significance for improving the comprehensive performance of the lithium iron phosphate positive electrode material, and particularly has remarkable effect for improving the high-current charge-discharge capacity and the low-temperature performance of the material. The modified material can be charged and discharged at 10-30 ℃ and the discharge capacity at-20 ℃ is not less than 75% of the normal-temperature discharge capacity, and is suitable for power electricity.
The above patent adopts polypyrrole, polythiophene and polyaniline as the molecules to coat the surface of the lithium iron phosphate anode material, the whole modification method in the process steps is complicated, the lithium iron phosphate anode material is required to be placed in a special discharge plasma container, and in a special production line, the mode is complicated in operation, continuous production cannot be carried out, and the production efficiency is low.
Disclosure of Invention
The invention aims to provide a surface modification method of a lithium iron phosphate positive electrode material, so as to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: the surface modification method of the lithium iron phosphate anode material comprises the following steps of;
step one: preparing a lithium iron phosphate foil;
step two: placing a lithium iron phosphate foil roll into a lithium iron phosphate modification device;
step three: cleaning the modified surface of the modified lithium iron phosphate foil, drying and then rewinding;
the lithium iron phosphate modification equipment in the second step comprises a frame, wherein the top of the frame is fixedly connected with a cover plate, the top of the cover plate is provided with two spraying mechanisms, and the front side and the rear side of one end of the frame are respectively fixedly connected with an end frame; a roller is rotationally connected between the two end frames, a feeding roller, a first folding roller, a transmission roller set, a second folding roller, a third folding roller, a roundabout roller set, a compression roller and an output roller which are driven by a motor are sequentially arranged in the frame from one side to the other side of the roller, the feeding roller, the transmission roller set, the third folding roller and the output roller are positioned at the same height, the first folding roller and the second folding roller are positioned below the feeding roller, one of the spraying mechanisms is arranged in a triangle area formed by the feeding roller, the first folding roller and the transmission roller set and surrounds the first folding roller, the other spraying mechanism is arranged in a triangular area formed by the transmission roller group, the second folding roller and the third folding roller and surrounds the second folding roller, the roundabout roller group comprises two folding rollers, the two folding rollers are obliquely arranged between the pressing roller and the third folding roller, the position of the folding roller close to the third folding roller is lower than that of the other folding roller, a vibrating mechanism is arranged between the third folding roller and the folding roller with higher position in the frame, a waste liquid collecting mechanism is arranged between the folding roller and the pressing roller with lower position, and the waste liquid collecting mechanism is connected below the folding roller with higher position.
Still further, spraying mechanism is including embedding the medicament case at apron top and fix the recovery cover of both sides inner wall around the frame, medicament case top plug has the charging plug, recovery cover top fixedly connected with backplate, a plurality of shower nozzles are installed to backplate top equidistance embedding, medicament case bottom has the medicament pump through the pipe connection, and the output of medicament pump passes through the pass medicine union coupling on each shower nozzle.
Furthermore, the bottom of the recovery cover is fixedly connected with a discharge pipe, the discharge pipe penetrates through the bottom of the frame, and the bottom of the guard plate is fixedly connected with a contact hair roller.
Further, the medicine tank of the spraying mechanism surrounding the first folding roller is filled with a reducing sugar solution, and the medicine tank of the spraying mechanism surrounding the second folding roller is filled with a silver-ammonia solution after being prepared.
Further, the reducing sugar solution is one or more of glucose, fructose, galactose, lactose and maltose with the concentration of 10% -15%.
Further, the silver ammonia solution preparing step comprises the following steps:
s1: preparing silver nitrate solution with the concentration of 2% -5% and storing the silver nitrate solution in a container;
s2: adding sodium hydroxide solution with the concentration of 3% -5% into a container for storing silver nitrate solution until no sediment is produced;
s3: adding ammonia water with the concentration of 3% -5% into a container until the precipitate is completely dissolved, and then obtaining silver ammonia solution.
Further, the conveying roller set comprises two conveying rollers which are arranged in parallel, a plurality of first heating rods are arranged in the frame and positioned between the two conveying rollers, and second heating rods are respectively arranged in the frame and positioned at one side of the vibrating mechanism close to the third folding roller and one side of the vibrating mechanism close to the folding roller; the recovery mechanism is installed at the embedded top of the cover plate, the recovery mechanism comprises a gas collecting hood, the gas collecting hood is embedded in the top of the cover plate, the gas collecting hood is located above the first heating rod, a plurality of sub-suction pipes are installed at the top of the gas collecting hood at equal intervals, and the top of the sub-suction pipes are connected with recovery pipes together.
Still further, vibration mechanism includes vibration cover and installs at the positive driving motor of frame, and the front and back both ends of vibration cover are fixed on the inner wall around the frame, and the vibration cover includes cylindrical cover and square cover, square cover is fixed at the outer wall of cylindrical cover, and the both sides inner wall of square cover is fixedly connected with spacing piece respectively, the top and the bottom of spacing piece are fixedly connected with a plurality of contact springs respectively, square cover inside slides and is provided with the conflict piece, and the conflict piece is the worker shape structure, spacing piece is located the groove of conflict piece both sides, contact spring is because conflict piece fixed connection, the inside centre of a circle department rotation of cylindrical cover is connected with the center pin, the outer wall equidistance fixedly connected with eccentric block of center pin, driving motor's output runs through the positive rear drive center pin of frame and rotates.
Still further, waste liquid collection mechanism includes and collects the cover, collects the cover and fixes on the frame front and back both sides inner wall, collect the positive fixedly connected with output tube of cover, the output tube other end runs through the frame is positive, collect the cover top be close to one side fixedly connected with doctor-bar of turning roller.
Still further, frame bottom fixedly connected with chassis, control panel is installed to the frame front, feed roll, first roll-over, transmission roller group, second roll-over, third roll-over, circuitous roller group, compression roller and output roller, two spraying mechanism, vibration mechanism and waste liquid collection mechanism respectively with control panel electric connection.
Compared with the prior art, the invention has the beneficial effects that:
according to the surface modification method of the lithium iron phosphate positive electrode material, two spraying mechanisms are used for spraying two medicaments, different medicaments are sprayed out respectively, the first spraying is a reducing sugar solution, the other spraying is a newly configured silver ammonia solution, so that a silver mirror can be generated on one side of a lithium iron phosphate foil by utilizing the reaction of the two solutions, a silver layer is attached to the surface of the lithium iron phosphate foil, the high conductivity of silver is utilized, the conductivity of the positive electrode can be improved, and the charge and discharge capacity and the low temperature resistance of a battery using the modified lithium iron phosphate foil as the positive electrode are improved.
Meanwhile, the lithium iron phosphate foil reacted out is vibrated through the vibration mechanism, the central shaft is driven to rotate by the driving motor, the eccentric block on the central shaft is continuously in high-frequency interference with the interference block, so that the interference block can vibrate at a tiny high frequency, the solvent of solid glucose can be accelerated, the shaking operation in a laboratory is simulated, the reaction speed can be improved, and the produced silver layer is more uniform and reliable by matching with the heating of the second heating rod.
Drawings
FIG. 1 is a schematic diagram of the overall structure of the present invention;
FIG. 2 is a schematic view of the internal structure of the present invention;
FIG. 3 is a schematic view of a spray mechanism according to the present invention;
FIG. 4 is a schematic view of a recycling mechanism according to the present invention;
FIG. 5 is a schematic diagram of a vibration mechanism according to the present invention;
FIG. 6 is an enlarged schematic view of the structure of FIG. 5A according to the present invention;
FIG. 7 is a schematic diagram of a cross-sectional position of a vibration mechanism of the present invention;
FIG. 8 is a schematic view of a waste liquid collecting mechanism according to the present invention;
FIG. 9 is a graph of temperature versus battery efficiency for this comparison;
fig. 10 is a graph of discharge time versus battery voltage for this comparison.
In the figure: 1. a frame; 2. a cover plate; 3. a spraying mechanism; 301. a medicament box; 302. a feeding plug; 303. a medicament pump; 304. a drug delivery tube; 305. a spray head; 306. a recovery cover; 307. a guard board; 308. contacting the fur roller; 309. a discharge pipe; 4. a recovery mechanism; 401. a gas collecting hood; 402. a sub-suction pipe; 403. a recovery pipe; 5. a vibration mechanism; 501. a vibration cover; 502. a collision block; 503. a driving motor; 504. a limiting piece; 505. a contact spring; 506. a central shaft; 507. an eccentric block; 6. a waste liquid collection mechanism; 601. a collection cover; 602. an output pipe; 603. a wiper blade; 7. a control panel; 8. a chassis; 9. an end frame; 10. a roller; 11. a feed roller; 12. a first folding roller; 13. a transport roller group; 14. a second folding roller; 15. a third folding roller; 16. a detour roller set; 17. a press roller; 18. an output roller; 20. a second heating rod; 21. a first heating rod.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, in the description of the present invention, the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements to be referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Furthermore, it should be understood that the dimensions of the various elements shown in the figures are not drawn to actual scale, e.g., the thickness or width of some layers may be exaggerated relative to other layers for ease of description.
It should be noted that like reference numerals and letters refer to like items in the following figures, and thus once an item is defined or illustrated in one figure, no further detailed discussion or description thereof will be necessary in the following description of the figures.
Taking a conventional type of 1860 battery taking lithium iron phosphate as a positive electrode material as an example, the battery is of a multi-layer structure, wherein a positive electrode foil taking lithium iron phosphate as the positive electrode material and a negative electrode foil taking a carbon material as the negative electrode material are included, a diaphragm is arranged between the positive electrode foil and the negative electrode foil for insulation, electrolyte is filled in the battery, a battery body is formed under the wrapping of a metal shell, the device mainly aims at the lithium battery taking the positive electrode material as a foil, the lithium iron phosphate positive electrode material foil is firstly required to be manufactured and obtained during production and manufacture, the lithium iron phosphate positive electrode material foil belongs to the existing mature technology, and a coating method is mainly used for coating lithium iron phosphate on a current collector to form a lithium iron phosphate positive electrode sheet, and then the surface modification method of the lithium iron phosphate positive electrode sheet is used for improving the charging and discharging capacity and the low temperature resistance effect of the lithium iron phosphate.
As shown in fig. 1 to 10, the present invention provides a technical solution: the surface modification method of the lithium iron phosphate anode material comprises the following steps of;
step one: preparing a lithium iron phosphate foil;
step two: placing the lithium iron phosphate foil roll into lithium iron phosphate modification equipment, wherein the modified object is a positive foil of lithium iron phosphate;
step three: cleaning the modified surface of the modified lithium iron phosphate foil, drying and then rewinding, wherein the cleaning aim is to remove the residual medicament on the surface of the modified foil, so that a clean modified lithium iron phosphate foil anode material is obtained after drying;
the lithium iron phosphate modification equipment in the second step comprises a frame 1, wherein the top of the frame 1 is fixedly connected with a cover plate 2, the top of the cover plate 2 is provided with two spraying mechanisms 3, and the front side and the rear side of one end of the frame 1 are respectively fixedly connected with an end frame 9; the two end frames 9 are rotatably connected with a winding roller 10, a feeding roller 11, a first folding roller 12, a transmission roller group 13, a second folding roller 14, a third folding roller 15, a roundabout roller group 16, a compression roller 17 and an output roller 18 which are driven by a motor are sequentially arranged from one side to the other side of the winding roller 10 in the frame 1, the feeding roller 11, the transmission roller group 13, the third folding roller 15 and the output roller 18 are positioned at the same height, the first folding roller 12 and the second folding roller 14 are positioned below the feeding roller 11, one spraying mechanism 3 is arranged in a triangular area formed by the feeding roller 11, the first folding roller 12 and the transmission roller group 13 and surrounds the first folding roller 12, the other spraying mechanism 3 is arranged in a triangular area formed by the transmission roller group 13, the second folding roller 14 and the third folding roller 15 and surrounds the second folding roller 14, the roundabout roller group 16 comprises two turning rollers, the two turning rollers are obliquely arranged between the compression roller 17 and the third folding roller 15, the position of the roller close to the third folding roller 15 is lower than the other turning roller, the inner side of the frame 1 is positioned between the high-turning roller 5 and the lower turning roller 6 is arranged at the position of the lower turning roller 6, and the waste liquid is collected at the position of the lower turning mechanism is arranged between the high-turning roller 6 and the lower turning roller 6.
It should be noted that when the device is used, firstly, a coiled lithium iron phosphate foil is required to be placed on the feeding roller 11, then, the end of the coiled lithium iron phosphate foil is processed, and then, a silver mirror is generated on one side of the lithium iron phosphate foil through the upper part of the feeding roller 11, the lower part of the first folding roller 12, the upper part of the conveying roller set 13, the lower part of the second folding roller 14, the upper part of the third folding roller 15 and the two sides of the roundabout roller set 16 in a manual guiding mode, and then, the two sides of the roundabout roller set are led out from the upper part of the output roller 18, and other devices are connected to maintain tension, wherein the coiled lithium iron phosphate foil is required to be sprayed by two times through a spraying mechanism 3, different agents are sprayed respectively, the first spraying is a reducing sugar solution, the glucose solution is adopted this time, and the other silver ammonia solution is newly configured, so that a silver mirror is generated on one side of the lithium iron phosphate foil by utilizing the reaction of the two, and then, a silver layer is attached to the surface of the lithium iron phosphate foil, thereby, the high conductivity of silver is utilized, the positive electrode conductivity can be improved, and the charging and low-temperature discharge resistance of the battery using the modified lithium iron phosphate foil can be positive.
Referring to fig. 3, the spraying mechanism 3 includes a medicine tank 301 embedded in the top of the cover plate 2 and a recovery cover 306 fixed on the inner walls of the front and rear sides of the frame 1, the top of the medicine tank 301 is plugged with a feeding plug 302, the top of the recovery cover 306 is fixedly connected with a guard 307, a plurality of spray heads 305 are installed on the top of the guard 307 in an equidistant embedded manner, the bottom of the medicine tank 301 is connected with a medicine pump 303 through a pipeline, the output end of the medicine pump 303 is connected to each spray head 305 through a medicine delivery pipe 304, the bottom of the recovery cover 306 is fixedly connected with a discharge pipe 309, the discharge pipe 309 penetrates through the bottom of the frame 1, the bottom of the guard 307 is fixedly connected with a contact hair roller 308, the medicine tank 301 of the spraying mechanism 3 surrounding the first folding roller 12 is filled with a reducing sugar solution, the medicine tank 301 of the spraying mechanism 3 surrounding the second folding roller 14 is filled with a prepared silver-ammonia solution, the reducing sugar solution is one or a mixture solution of glucose, fructose, galactose, lactose and maltose with a concentration of 10% -15%, and the silver-ammonia solution is prepared by the steps of: s1: preparing silver nitrate solution with the concentration of 2% -5% and storing the silver nitrate solution in a container; s2: adding sodium hydroxide solution with the concentration of 3% -5% into a container for storing silver nitrate solution until no sediment is produced; s3: adding ammonia water with the concentration of 3% -5% into a container until the precipitate is completely dissolved, and then obtaining silver ammonia solution.
Note that reducing sugar means a sugar having reducing property, and among the sugar, a monosaccharide having a free aldehyde group or ketone group in the molecule and a disaccharide having a free aldehyde group have reducing property. The reducing sugar mainly comprises glucose, fructose, galactose, lactose, maltose and the like, and other compounds which can generate free aldehyde groups can be used in the preparation of the present application, and the equipment mainly uses glucose as an initial preparation to be sprayed on the surface of the lithium iron phosphate foil because the glucose has higher yield, lower cost and almost no pollution, wherein the chemical reaction formula of silver nitrate and sodium hydroxide in the preparation process of the silver ammonia solution is as follows:
AgNO3+NaOH=AgOH↓+NaNO3
then adding 3% -5% ammonia water into the container, wherein the chemical reaction formula is as follows:
AgOH + 2NH 3 .H 2 O =Ag（NH 3 ） 2 OH + 2H 2 O
the chemical reaction formula for the subsequent reaction with glucose using silver ammonia solution is:
CH2OH（CHOH）4CHO+2OH→CH2OH（CHOH）4COONH4+2Ag↓+3NH3+H2O
thereby producing a silver mirror, which is used in many cases for electroless silver plating operations.
It should be noted that in the process of spraying by using the spraying mechanism 3, the chemical is respectively transferred to each spray head 305 by pumping air of the chemical pump 303, so that the chemical is uniformly adhered to the surface of the lithium iron phosphate foil, and the excessive chemical is recovered and processed by the discharge pipe 309 at the bottom of the recovery cover 306.
Referring to fig. 2 and 4, the conveying roller set 13 includes two conveying rollers arranged in parallel with each other, a plurality of first heating rods 21 are installed in the frame 1 at positions between the two conveying rollers, and second heating rods 20 are respectively installed in the frame 1 at one side of the vibrating mechanism 5 near the third folding roller 15 and one side near the folding roller; the recovery mechanism 4 is installed in the embedded mode at the top of the cover plate 2, the recovery mechanism 4 comprises a gas collecting hood 401, the gas collecting hood 401 is embedded in the top of the cover plate 2, the gas collecting hood 401 is located above the first heating rod 21, a plurality of sub-suction pipes 402 are installed at the top of the gas collecting hood 401 at equal intervals, and recovery pipes 403 are connected to the tops of the sub-suction pipes 402.
It should be noted that, after the first spraying of the reagent, in order to ensure the adhesion effect of the glucose solution and to increase the concentration of the solution in the subsequent reaction to increase the reaction speed, a plurality of first heating rods 21 are installed at positions between the two material conveying rollers, the purpose of which is to evaporate moisture in the glucose solvent, so that the glucose solid particles adhere to the surface of the lithium iron phosphate foil, after contacting the silver-ammonia solution, they are dissolved in the silver-ammonia solution, the two solutions are prevented from mixing to reduce the concentration of each solute, the temperature of the lithium iron phosphate foil is heated to 40-50 ℃ by the second heating rod 20, the silver-mirror reaction can be accelerated at this temperature, and the recovery mechanism 4 is provided to recover water vapor by using the gas collecting hood 401, and the exhaust gas is transmitted by connecting the gas pump by using the recovery tube 403.
Referring to fig. 5 to 7, the vibration mechanism 5 includes a vibration cover 501 and a driving motor 503 mounted on the front surface of the frame 1, the front and rear ends of the vibration cover 501 are fixed on the front and rear inner walls of the frame 1, the vibration cover 501 includes a cylindrical cover and a square cover, the square cover is fixed on the outer wall of the cylindrical cover, two side inner walls of the square cover are respectively fixedly connected with a limiting piece 504, the top and bottom of the limiting piece 504 are respectively fixedly connected with a plurality of contact springs 505, the inside of the square cover is slidably provided with a collision block 502, the collision block 502 is in an i-shaped structure, the limiting piece 504 is located in grooves on two sides of the collision block 502, the contact springs 505 are fixedly connected with the central shaft 506 due to the collision block 502, the center of the inside of the cylindrical cover is rotationally connected with the central shaft 506, the outer wall of the central shaft 506 is fixedly connected with an eccentric block 507 at equal intervals, and the output end of the driving motor 503 penetrates the front surface of the frame 1 to drive the central shaft 506.
In order to further improve the speed of silver mirror reaction, be provided with vibration mechanism 5 specially and vibrate the lithium iron phosphate foil that reacts, utilize driving motor 503 to drive center pin 506 and rotate, the continuous high frequency of eccentric piece 507 on the center pin 506 is contradicted on conflict piece 502 for conflict piece 502 can carry out the vibration of tiny high frequency, thereby can accelerate solid glucose's solvent, the operation of rocking in the simulation laboratory makes the silver layer of production more even reliable.
Referring to fig. 8, the waste liquid collecting mechanism 6 includes a collecting cover 601, the collecting cover 601 is fixed on inner walls of front and rear sides of the frame 1, an output pipe 602 is fixedly connected to the front of the collecting cover 601, the other end of the output pipe 602 penetrates through the front of the frame 1, and a scraping blade 603 is fixedly connected to one side, close to the turning roller, of the top of the collecting cover 601.
It should be noted that a lot of waste liquid remains on the reacted lithium iron phosphate foil, and the waste liquid passes through the turning of the winding roller set 16, is scraped into the collecting cover 601 by the scraping blade 603 in the waste liquid collecting mechanism 6, and is then transported out for recycling by the output pipe 602.
Referring to fig. 1, a chassis 8 is fixedly connected to the bottom of a frame 1, a control panel 7 is mounted on the front surface of the frame 1, and a feeding roller 11, a first folding roller 12, a transmission roller set 13, a second folding roller 14, a third folding roller 15, a roundabout roller set 16, a compression roller 17 and an output roller 18, two spraying mechanisms 3, a vibration mechanism 5 and a waste liquid collecting mechanism 6 are respectively and electrically connected with the control panel 7.
The control panel 7 is used as a control main body of the whole equipment, and can control the transmission speed of the lithium iron phosphate foil, the medicine spraying quantity of the spraying mechanism 3 and the vibration frequency of the vibration mechanism 5, and various parameters can be flexibly controlled according to different silver plating requirements.
In order to verify that the modified lithium iron phosphate electrode has higher discharge efficiency and low temperature resistance, 12V/8Ah with the same specification on the market is selected, a 4S1P serial connection mode is adopted, a battery pack is adopted, a positive electrode material is a conventional lithium iron phosphate battery pack and a ternary lithium battery pack is arranged to be compared, and low temperature efficiency and voltage efficiency tests are carried out, wherein fig. 9 is a graph of battery efficiency at three different temperatures, the efficiency of the modified lithium iron phosphate electrode at the low temperature is higher, fig. 9 is a voltage change unit/V and a time unit/h of the battery under continuous discharge, and compared with the conventional lithium iron phosphate electrode, the modified lithium iron phosphate electrode has higher efficient stability and discharge capability, and the ternary lithium battery is also stronger in stability due to the material characteristics.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended embodiments and equivalents thereof.
Claims (8)
1. The surface modification method of the lithium iron phosphate anode material is characterized by comprising the following steps of: comprises the following steps of;
step one: preparing a lithium iron phosphate foil;
step two: placing a lithium iron phosphate foil roll into a lithium iron phosphate modification device;
step three: cleaning the modified surface of the modified lithium iron phosphate foil, drying and then rewinding;
the lithium iron phosphate modification equipment in the second step comprises a frame (1), wherein a cover plate (2) is fixedly connected to the top of the frame (1), two spraying mechanisms (3) are arranged on the top of the cover plate (2), and end frames (9) are respectively and fixedly connected to the front side and the rear side of one end of the frame (1); a rolling roller (10) is rotatably connected between the two end frames (9), a feeding roller (11), a first folding roller (12), a transmission roller set (13), a second folding roller (14), a third folding roller (15), a winding roller set (16), a compression roller (17) and an output roller (18) which are driven by a motor are sequentially arranged inside the frame (1) from one side to the other side of the rolling roller (10), the feeding roller (11), the transmission roller set (13), the third folding roller (15) and the output roller (18) are positioned at the same height, the first folding roller (12) and the second folding roller (14) are positioned below the feeding roller (11), one spraying mechanism (3) is arranged in a triangular area formed by the feeding roller (11), the first folding roller (12) and the transmission roller set (13) and surrounds the first folding roller (12), the other spraying mechanism (3) is arranged in a triangular area formed by the transmission roller set (13), the second folding roller (14) and the third folding roller (15) and surrounds the second folding roller (14), the other spraying mechanism (3) is arranged in a triangular area formed by the transmission roller set (14) and surrounds the third folding roller (15), the second folding roller (14) and the winding roller (16) is arranged between the second folding roller (15) and the third folding roller (15) and the winding roller (15) and the second folding roller (16) and the third folding roller (13) and the winding roller is arranged at a lower position, a vibration mechanism (5) is arranged between the third turning roller (15) and the turning roller with higher position in the frame (1), a waste liquid collecting mechanism (6) is arranged between the turning roller and the pressing roller (17) with lower position, and the waste liquid collecting mechanism (6) is accepted under the turning roller with higher position;
the spraying mechanism (3) comprises a medicament box (301) embedded in the top of the cover plate (2) and recovery covers (306) fixed on the inner walls of the front side and the rear side of the frame (1), a feeding plug (302) is plugged in the top of the medicament box (301), a guard plate (307) is fixedly connected to the top of the recovery cover (306), a plurality of spray heads (305) are installed at the top of the guard plate (307) in an equidistant embedded mode, a medicament pump (303) is connected to the bottom of the medicament box (301) through a pipeline, the output end of the medicament pump (303) is connected to each spray head (305) through a medicament delivery pipe (304), a reducing sugar solution is filled in the medicament box (301) of the spraying mechanism (3) surrounded by the first folding roller (12), and a silver-ammonia solution arranged after completion is filled in the medicament box (301) of the spraying mechanism (3) surrounded by the second folding roller (14).
2. The method for surface modification of lithium iron phosphate positive electrode material according to claim 1, characterized in that: the bottom of the recovery cover (306) is fixedly connected with a discharge pipe (309), the discharge pipe (309) penetrates through the bottom of the frame (1), and the bottom of the guard plate (307) is fixedly connected with a contact hair roller (308).
3. The method for surface modification of lithium iron phosphate positive electrode material according to claim 1, characterized in that: the reducing sugar solution is one or more mixture solutions of glucose, fructose, galactose, lactose and maltose with the concentration of 10% -15%.
4. The method for surface modification of lithium iron phosphate positive electrode material according to claim 1, characterized in that: the silver ammonia solution preparation steps are as follows:
s1: preparing silver nitrate solution with the concentration of 2% -5% and storing the silver nitrate solution in a container;
s2: adding sodium hydroxide solution with the concentration of 3% -5% into a container for storing silver nitrate solution until no sediment is produced;
s3: adding ammonia water with the concentration of 3% -5% into a container until the precipitate is completely dissolved, and then obtaining silver ammonia solution.
5. The method for surface modification of lithium iron phosphate positive electrode material according to claim 1, characterized in that: the conveying roller set (13) comprises two conveying rollers which are arranged in parallel, a plurality of first heating rods (21) are arranged in the frame (1) at positions between the two conveying rollers, and second heating rods (20) are respectively arranged in the frame (1) at one side of the vibrating mechanism (5) close to the third folding roller (15) and one side of the vibrating mechanism close to the folding roller; the utility model discloses a recovery device, including apron (2), apron (2) top embedding is installed recovery mechanism (4), recovery mechanism (4) are including gas collecting channel (401), and gas collecting channel (401) embedding is at apron (2) top, gas collecting channel (401) are located the top of first heating rod (21), a plurality of branch straw (402) are installed to gas collecting channel (401) top equidistance, and branch straw (402) top is connected with recovery pipe (403) jointly.
6. The method for surface modification of lithium iron phosphate positive electrode material according to claim 1, characterized in that: vibration mechanism (5) are including vibrating cover (501) and installing positive driving motor (503) at frame (1), and both ends are fixed around frame (1) on the inner wall around vibrating cover (501), and vibrating cover (501) are including cylindrical cover and square cover, square cover is fixed at the outer wall of cylindrical cover, and the both sides inner wall of square cover is spacing piece (504) fixedly connected with respectively, the top and the bottom of spacing piece (504) are a plurality of contact spring (505) respectively fixedly connected with, square cover inside slip is provided with conflict piece (502), and conflict piece (502) are the worker's shape structure, spacing piece (504) are located the groove of conflict piece (502) both sides, contact spring (505) are because conflict piece (502) fixed connection, the inside centre of a circle department rotation of cylindrical cover is connected with center pin (506), the equidistance fixedly connected with eccentric block (507) of the outer wall of center pin (506), driving motor (503) output runs through frame (1) openly back driving center pin (506) and rotates.
7. The method for surface modification of lithium iron phosphate positive electrode material according to claim 1, characterized in that: the waste liquid collecting mechanism (6) comprises a collecting cover (601), the collecting cover (601) is fixed on the inner walls of the front side and the rear side of the frame (1), an output pipe (602) is fixedly connected to the front side of the collecting cover (601), the other end of the output pipe (602) penetrates through the front side of the frame (1), and a scraping blade (603) is fixedly connected to one side, close to the turning roller, of the top of the collecting cover (601).
8. The method for surface modification of lithium iron phosphate positive electrode material according to claim 1, characterized in that: the novel spraying device is characterized in that the bottom of the frame (1) is fixedly connected with an underframe (8), a control panel (7) is arranged on the front surface of the frame (1), and the feeding roller (11), the first folding roller (12), the transmission roller set (13), the second folding roller (14), the third folding roller (15), the roundabout roller set (16), the compression roller (17) and the output roller (18), and the two spraying mechanism (3), the vibration mechanism (5) and the waste liquid collecting mechanism (6) are respectively and electrically connected with the control panel (7).
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| CN115084529A (en) * | 2022-08-16 | 2022-09-20 | 四川富临新能源科技有限公司 | Surface modification method of lithium iron phosphate positive electrode material |
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| JP2005152827A (en) * | 2003-11-27 | 2005-06-16 | Advance:Kk | Apparatus for forming silver mirror thin film, method for forming thin film using the apparatus, and method for forming coating film |
| CN101222047B (en) * | 2008-01-14 | 2010-12-29 | 浙江大学 | Cathode material of thin film lithium ion battery and method for producing the same |
| CN102157731B (en) * | 2011-03-18 | 2015-03-04 | 上海交通大学 | Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material |
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| CN115084529A (en) * | 2022-08-16 | 2022-09-20 | 四川富临新能源科技有限公司 | Surface modification method of lithium iron phosphate positive electrode material |
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