CN110797530B - High-voltage lithium cobalt oxide graphite battery and preparation method thereof - Google Patents
High-voltage lithium cobalt oxide graphite battery and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage lithium cobaltate/graphite battery, which comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte; the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, wherein the positive active material layer comprises a positive active material, a conductive agent, a positive binder and a positive prefilming additive, and the positive active material is doped and coated with modified lithium cobaltate; the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer coated on the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material, a negative electrode binder and a dispersing agent, and the negative electrode active material is carbon coated graphite; the charge cut-off voltage of the high voltage lithium cobaltate/graphite cell was 4.48V. The high-voltage lithium cobaltate/graphite battery prepared by the invention has high energy density, good cycle performance, high safety performance and quick charge and low-temperature charge capability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage lithium cobaltate/graphite battery and a preparation method thereof.
Background
The lithium cobaltate has the advantages of stable and reliable preparation process, high charge and discharge capacity, stable charge and discharge voltage, multiple times of recycling and the like, is a widely used lithium ion battery anode material at present, and particularly occupies absolute predominance in a 3C battery.
The 3C product has urgent demands on the endurance and charging speed, and the improvement of the energy density of the battery cell becomes necessary under the condition of not increasing the volume of the battery cell.
The gram capacity of lithium cobaltate in the existing battery cell is about 172mAh/g (the charge cut-off voltage is 4.40V, and the platform voltage is 3.83V). However, when the charging voltage of the battery is increased (i.e., the charging cut-off voltage is increased from 4.40V to 4.48V, the gram capacity can be increased to 185mAh/g, and the platform voltage is 3.88V), excessive lithium removal of lithium cobaltate is caused, and charge imbalance in a high lithium removal state can cause expansion and shrinkage of a crystal structure, so that a distorted cell and dislocation occur, stability of the crystal structure of lithium cobaltate is reduced, and cycle performance is greatly reduced. In addition, under the high voltage condition, co 4+ Carrying out oxidation-reduction reaction with carbonate electrolyte to lead the electrolyte to decompose and produce gas; co production at the same time 2+ The dissolution leads the lithium cobaltate to generate irreversible capacity attenuation, and the cycle performance of the battery core is seriously shortened; at high temperatures, the process releases a large amount of heat and even explodes in severe cases, and the safety performance of the battery is also faced with great challenges. Therefore, the voltage of the battery cell is only increased to 4.48V, and the actual performance requirement cannot be met when the lithium cobaltate is not treated.
In addition, the negative electrode material of the existing lithium cobaltate/graphite battery is generally artificial graphite which is not subjected to carbon coating treatment, is not beneficial to rapid diffusion of lithium ions, is easy to separate out lithium during high-current rapid charging, has potential safety hazards, and is difficult to meet actual demands.
Therefore, the existing battery system cannot meet the requirements of the 4.48V high-voltage lithium cobalt oxide/graphite battery on the cycle life and the charging speed. Therefore, the improvement of the existing lithium cobalt oxide battery system to reduce the oxidizing property of the surface of lithium cobalt oxide, improve the structural stability of lithium cobalt oxide and meet the quick charge requirement of the battery has important significance.
Disclosure of Invention
One of the objects of the present invention is: the high-voltage lithium cobaltate/graphite battery is high in energy density, good in cycle performance and high in safety performance, and has the capability of quick charge and low-temperature charge.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a high-voltage lithium cobaltate/graphite battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte; the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, wherein the positive active material layer comprises a positive active material, a conductive agent, a positive binder and a positive prefilming additive, and the positive active material is doped and coated with modified lithium cobaltate; the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer coated on the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material, a negative electrode binder and a dispersing agent, and the negative electrode active material is carbon-coated graphite; the high voltage lithium cobaltate/graphite battery has a charge cut-off voltage of 4.48V. The positive electrode active material is doped and coated with modified lithium cobalt oxide, so that excessive lithium removal of lithium cobalt oxide can be avoided, and the structural stability of lithium cobalt oxide crystals can be improved. In the process of preparing the positive electrode slurry, the positive electrode pre-film forming additive is attached to the surface of the doped and coated modified lithium cobalt oxide particles along with the conductive agent, so that the contact between the surface of the positive electrode and the electrolyte is reduced, and the oxidation of the 4-valent cobalt to the electrolyte is prevented to a certain extent. Because conventional graphite cannot meet the requirement of quick charge, the negative electrode material is designed into carbon-coated graphite, and the quick charge requirement of a high-voltage lithium cobaltate/graphite battery can be met. Through the optimization of the battery system, the charge cut-off voltage of the lithium cobaltate/graphite battery can reach 4.48V, and the situation that the circulation performance is reduced due to the occurrence of the inflation of the battery is avoided.
As an improvement of the high-voltage lithium cobaltate/graphite battery, the preparation method of the doped coated modified lithium cobaltate comprises the following steps:
dissolving first cobalt salt and aluminum salt in deionized water, and carrying out coprecipitation reaction and heat treatment to obtain aluminum-doped first cobaltosic oxide particles;
dissolving second cobalt salt and aluminum salt in deionized water, and carrying out coprecipitation reaction and heat treatment to obtain aluminum-doped second cobaltosic oxide particles;
mixing a lithium source, the first cobaltosic oxide particles and a first additive, and performing ball milling, calcination, crushing and sieving to obtain first coated lithium cobaltate particles;
mixing a lithium source, the second cobaltosic oxide particles and the first additive, and performing ball milling, calcination, crushing and sieving to obtain first coated second lithium cobaltate particles;
mixing the first lithium cobaltate particles, the second lithium cobaltate particles and the second additive for secondary coating, and performing ball milling, calcination, crushing and sieving to obtain doped coated modified lithium cobaltate;
wherein the median particle size of the first cobaltosic oxide particles is greater than the median particle size of the second cobaltosic oxide particles; the median particle size of the first lithium cobaltate particles is greater than the median particle size of the second lithium cobaltate particles.
Preferably, the first cobalt salt is cobalt sulfate, the aluminum salt is aluminum sulfate, and the mass ratio of the aluminum to the cobalt is 0.9-1.1:100; the second cobalt salt is cobalt sulfate, the aluminum salt is aluminum sulfate, and the mass ratio of the aluminum to the cobalt is 0.9-1.1:100. The Al doping amount in the first cobaltosic oxide particles is 5500-6500ppm, the median particle diameter is 11-20 mu m, the Al doping amount in the second cobaltosic oxide particles is 5500-6500ppm, and the median particle diameter is 2-8 mu m.
The invention stabilizes the crystal structure of lithium cobaltate by doping proper amount of Al, and can inhibit/weaken O 3 Hexagonal phase → H 1-3 The phase change of the secondary monoclinic phase improves the structural stability of the lithium cobaltate in the circulation process, prevents the circulation performance from being reduced due to the collapse of the lithium cobaltate structure under high voltage, and can also improve the discharge energy density. The lithium source forming the first coating layer can synchronously perform lithium deintercalation, so that lithium ions reaching the negative electrode are increased, and the battery has higher energy density. The inner layer of the material doped with the coated modified lithium cobaltate is made of two lithium cobaltate materials with different particle sizes, and the outermost layer is a new solid solution layer formed by coating the second additive, so that the contact between the cobalt with the valence 4 and the electrolyte is reduced, and the oxidizing property of the cobalt oxide to the electrolyte is reduced. The preparation method comprises the steps of preparing lithium cobaltate particles with larger particle size and smaller particle size respectively twice, and then sinteringThe preparation method can obtain the high-voltage lithium cobalt oxide anode material with higher compaction and high capacity.
As an improvement of the high-voltage lithium cobaltate/graphite battery of the present invention, the lithium source includes at least one of lithium carbonate, lithium hydroxide and lithium oxalate; the first additive comprises at least one element of Mg, al, ti or Zr; the second additive is a compound containing at least one element of Mg, al, ti or Zr. The second additive is at least one of oxide, fluoride, hydroxide, carbonate or phosphate containing at least one element of Mg, al, ti or Zr. The second additive includes, but is not limited to, at least one of magnesium oxide, magnesium fluoride, aluminum oxide, aluminum hydroxide.
As an improvement of the high-voltage lithium cobaltate/graphite battery, the mass ratio of the positive electrode active material to the positive electrode binder to the conductive agent to the positive electrode prefilming additive is 96-99:0.8-2:0.03-0.2. The content of the positive electrode prefilming additive is excessive, so that the contact between the surface of the positive electrode and electrolyte is reduced to a greater extent, but the migration rate of lithium ions is affected, and the low-temperature discharge performance of the battery is reduced; the content of the positive electrode prefilming additive is too small, the surface of the positive electrode is fully contacted with the electrolyte, the oxidation reaction of the 4-valent cobalt on the electrolyte is increased in a fully charged state, the electrolyte is decomposed, the electrolyte amount is reduced, byproducts are distributed at various positions in the battery, and the degradation of the battery cycle performance is accelerated.
As an improvement of the high-voltage lithium cobaltate/graphite battery, the positive electrode prefilming additive is polyvinylpyrrolidone. The anode slurry is added with a proper amount of anode prefilming additive which can be attached to the surface of doped and coated modified lithium cobalt oxide particles together with the conductive agent, so that the contact between the anode surface and the electrolyte is reduced, and the oxidation of the 4-valent cobalt to the electrolyte is prevented to a certain extent.
As an improvement of the high-voltage lithium cobaltate/graphite battery, the mass ratio of the negative electrode active material, the negative electrode binder and the dispersing agent is 97-98.5:0.8-1.5:0.7-1.5. The negative electrode binder is at least one of polystyrene-butadiene-acrylonitrile copolymer and polystyrene-acrylic ester copolymer.
As an improvement of the high-voltage lithium cobaltate/graphite battery, the dispersing agent is sodium carboxymethyl cellulose.
As an improvement of the high-voltage lithium cobaltate/graphite battery, the carbon-coated graphite has a median particle diameter D50 of 12-23 mu m, a specific surface area of 1.0-2.0 square meter/g and a graphitization degree of 93.0-94.0%.
As an improvement of the high voltage lithium cobaltate/graphite battery according to the invention, the electrolyte comprises a lithium salt, an organic solvent and a third additive. Wherein the lithium salt comprises lithium hexafluorophosphate, lithium difluorooxalato borate and other common lithium salts in the field, the concentration of the lithium hexafluorophosphate is 1.1-1.5 mol/L, and the concentration of the lithium difluorooxalato borate is 0.05-0.2 mol/L; the organic solvent includes, but is not limited to, at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, and propyl propionate. The third additive includes, but is not limited to, at least one of fluoroethylene carbonate, 1, 3-propane sultone, succinonitrile, hexadinitrile, ethylene glycol dipropionitrile ether and 1,3, 6-hexanetrinitrile.
Another object of the invention is: the preparation method of the high-voltage lithium cobalt oxide battery can reduce the oxidability of the surface of the lithium cobalt oxide and improve the structural stability of the lithium cobalt oxide, and comprises the following steps:
firstly, weighing doped coated modified lithium cobaltate, a positive electrode binder, a conductive agent and a positive electrode prefilming additive, adding the positive electrode binder into N-methyl pyrrolidone, dispersing into uniform first glue solution, adding the doped coated modified lithium cobaltate, the conductive agent and the positive electrode prefilming additive into the first glue solution, and stirring to obtain positive electrode slurry; and weighing carbon-coated graphite, a dispersing agent and a negative electrode binder, adding the dispersing agent into deionized water to be dispersed into a second glue solution, adding the carbon-coated graphite and the negative electrode binder into the second glue solution, and stirring to obtain the negative electrode slurry.
And secondly, uniformly coating the positive electrode slurry and the negative electrode slurry on a positive electrode current collector and a negative electrode current collector respectively, and rolling, slitting, welding a tab and rubberizing to obtain a positive plate and a negative plate.
And thirdly, laminating and/or winding the positive plate, the negative plate and the diaphragm to prepare a winding core, packaging, vacuum baking, injecting electrolyte, standing, high-temperature high-pressure formation, degassing, packaging and capacity division to obtain the high-voltage lithium cobalt oxide/graphite battery. Wherein the positive current collector is aluminum foil, and the negative current collector is copper foil. The conductive agent is at least one of conductive graphite, carbon nanotube and graphene. The positive electrode binder is polyvinylidene fluoride.
In the second step, the ratio of the capacity of the negative electrode active material per unit area to the capacity of the positive electrode active material per unit area is (1.025-1.075): 1. The ratio is too small, and lithium is easy to be separated from the battery core; the ratio is too large, and the cycle performance of the battery cell is reduced.
The beneficial effects of the invention include, but are not limited to: the invention carries out the optimization design on the whole high-voltage lithium cobaltate/graphite battery system, wherein the anode adopts doped cladding modified lithium cobaltate, can reduce the oxidability of the surface of the lithium cobaltate, improve the structural stability of the lithium cobaltate, improve the charge cut-off voltage of the battery from 4.40V to 4.48V, improve the gram capacity from 172mAh/g to 185mAh/g and improve the platform voltage from 3.83V to 3.88V; the anode prefilming additive is attached to the surface of the doped and coated modified lithium cobaltate particles along with the conductive agent, so that the contact between the anode surface and the electrolyte is reduced, and the oxidation of the 4-valent cobalt to the electrolyte is prevented to a certain extent. The negative electrode adopts carbon coated graphite, so that the quick charge function of the high-voltage lithium cobaltate/graphite battery is met, and the electrochemical performance is good. In conclusion, the high-voltage lithium cobaltate/graphite battery prepared by the method has the advantages of high energy density, good cycle performance, high safety performance and quick charge and low-temperature charge capability.
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the technical solution of the present invention will be clearly and completely described in conjunction with specific embodiments, and it is apparent that the described embodiments are 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.
Example 1
1) Preparation of doped coated modified lithium cobaltate:
dissolving first cobalt salt and aluminum salt in deionized water, and performing coprecipitation reaction and heat treatment to obtain aluminum-doped first cobaltosic oxide particles A;
dissolving second cobalt salt and aluminum salt in deionized water, and performing coprecipitation reaction and heat treatment to obtain aluminum-doped second cobaltosic oxide particles B;
mixing a lithium source, first cobaltosic oxide particles A and a first additive, and performing ball milling, calcination, crushing and sieving to obtain first coated lithium cobaltate particles C1;
mixing a lithium source, second cobaltosic oxide particles B and a first additive, and performing ball milling, calcination, crushing and sieving to obtain first coated second lithium cobaltate particles C2;
and fifthly, mixing the first lithium cobalt oxide particles C1, the second lithium cobalt oxide particles C2 and the second additive for secondary coating, and performing ball milling, calcination, crushing and sieving to obtain the doped coated modified lithium cobalt oxide.
Wherein, the median particle diameter of the first cobaltosic oxide particles A is larger than that of the second cobaltosic oxide particles B; the median particle diameter of the first lithium cobalt oxide particles C1 is larger than the median particle diameter of the second lithium cobalt oxide particles C2. The first cobalt salt is cobalt sulfate, the aluminum salt is aluminum sulfate, and the mass ratio of the aluminum to the cobalt is 0.9-1.1:100; the second cobalt salt is cobalt sulfate, the aluminum salt is aluminum sulfate, and the mass ratio of the aluminum to the cobalt is 0.9-1.1:100. The Al doping amount in the first cobaltosic oxide particles is 5500-6500ppm, the median particle diameter is 11-20 mu m, the Al doping amount in the second cobaltosic oxide particles is 5500-6500ppm, and the median particle diameter is 2-8 mu m. The lithium source includes at least one of lithium carbonate, lithium hydroxide, and lithium oxalate. The first additive comprises at least one element of Mg, al, ti or Zr. The second additive is at least one of oxide, fluoride, hydroxide, carbonate or phosphate containing at least one element of Mg, al, ti or Zr. The second additive includes, but is not limited to, at least one of magnesium oxide, magnesium fluoride, aluminum oxide, aluminum hydroxide, magnesium carbonate, aluminum phosphate, titanium dioxide, and zirconium oxide.
2) Preparation of a positive plate:
weighing doped coated modified lithium cobaltate, polyvinylidene fluoride, carbon nano tubes and polyvinylpyrrolidone according to the mass ratio of 98.2:1.0:0.65:0.15, adding polyvinylidene fluoride into N-methyl pyrrolidone to be dispersed into uniform glue solution, adding the doped coated modified lithium cobaltate, the carbon nano tubes and the polyvinylpyrrolidone into the glue solution, and stirring to prepare anode slurry;
and secondly, uniformly coating the anode slurry on two sides of an aluminum foil, rolling, cutting, welding tabs, rubberizing to obtain an anode plate, and finally baking and vacuum drying for later use.
3) Preparing a negative plate:
weighing carbon-coated graphite, sodium carboxymethyl cellulose and carboxyl styrene-butadiene rubber according to a mass ratio of 97.5:1.2:1.3, adding sodium carboxymethyl cellulose into deionized water to disperse into a glue solution, adding the carbon-coated graphite and the carboxyl styrene-butadiene rubber into the glue solution, and stirring to obtain negative electrode slurry;
and uniformly coating the negative electrode slurry on two sides of the copper foil, rolling, cutting, welding the tab and rubberizing to obtain a negative electrode plate, and finally baking and vacuum drying for later use.
The ratio of the capacity of the negative electrode active material per unit area to the capacity of the positive electrode active material per unit area is (1.025-1.075): 1.
4) Preparation of electrolyte:
in a glove box (O) 2 ＜2ppm，H 2 O < 3 ppm), ethylene carbonate, propylene carbonate, propyl propionate and diethyl carbonate are mixed according to the mass ratio of 2:2:1:5, uniformly mixing to prepare a nonaqueous organic solvent; then taking a nonaqueous organic solvent accounting for 73 percent of the total mass of the electrolyte, adding fluoroethylene carbonate accounting for 7 percent of the total mass of the electrolyte and 3 percent of 1, 3-propane sulfo-esterAcid lactone, 1% succinonitrile and 1% 1,3, 6-hexane trinitrile to obtain a mixed solution; and slowly adding a mixture of lithium hexafluorophosphate and lithium difluorooxalato borate accounting for 15% of the total mass of the electrolyte into the mixed solution to prepare a lithium salt solution with the concentration of 1.2mol/L of lithium hexafluorophosphate, and uniformly mixing to prepare the electrolyte.
5) Preparation of high voltage lithium cobaltate/graphite cell:
and (3) sequentially winding the positive plate, the diaphragm and the negative plate to obtain a bare cell, and packaging by an aluminum plastic film, baking, injecting liquid, standing, forming at high temperature and high pressure, degassing, packaging and capacity-dividing to obtain the high-voltage lithium cobalt oxide/graphite battery.
Example 2
The positive electrode sheet was prepared differently from example 1:
weighing the doped coated modified lithium cobaltate, polyvinylidene fluoride, superconducting carbon black and polyvinylpyrrolidone prepared in the embodiment 1 according to the mass ratio of 97.2:1.2:1.5:0.1, adding the polyvinylidene fluoride into N-methylpyrrolidone to be dispersed into uniform glue solution, adding the doped coated modified lithium cobaltate, carbon nano tubes and polyvinylpyrrolidone into the glue solution, and stirring to prepare anode slurry;
the remainder is the same as in example 1 and will not be described again here.
Example 3
The positive electrode sheet was prepared differently from example 1:
weighing the doped coated modified lithium cobaltate, polyvinylidene fluoride, carbon nano tubes and polyvinylpyrrolidone prepared in the embodiment 1 according to the mass ratio of 98.8:1.0:0.05:0.15, adding the polyvinylidene fluoride into N-methyl pyrrolidone to be dispersed into uniform glue solution, adding the doped coated modified lithium cobaltate, the carbon nano tubes and the polyvinylpyrrolidone into the glue solution, and stirring to prepare anode slurry;
the remainder is the same as in example 1 and will not be described again here.
Example 4
Unlike example 1, the following is:
preparing a negative plate:
weighing carbon-coated graphite, sodium carboxymethyl cellulose and carboxyl styrene-butadiene rubber according to a mass ratio of 98:1:1, adding sodium carboxymethyl cellulose into deionized water to disperse into a glue solution, adding the carbon-coated graphite and the carboxyl styrene-butadiene rubber into the glue solution, and stirring to obtain negative electrode slurry;
the remainder is the same as in example 1 and will not be described again here.
Example 5
The difference from example 1 is the preparation of positive and negative plates: the ratio of the negative electrode active material capacity per unit area to the positive electrode active material capacity per unit area is 1.025:1.
The remainder is the same as in example 1 and will not be described again here.
Example 6
The difference from example 1 is the preparation of positive and negative plates: the ratio of the negative electrode active material capacity per unit area to the positive electrode active material capacity per unit area is 1.075:1.
The remainder is the same as in example 1 and will not be described again here.
Comparative example 1
The positive electrode sheet was prepared differently from example 1:
weighing 4.40V lithium cobaltate, polyvinylidene fluoride, carbon nano tube and polyvinylpyrrolidone according to the mass ratio of 98.2:1.0:0.65:0.15, adding polyvinylidene fluoride into N-methyl pyrrolidone to be dispersed into uniform glue solution, adding 4.40V lithium cobaltate, carbon nano tube and polyvinylpyrrolidone into the glue solution, and stirring to prepare anode slurry;
the remainder is the same as in example 1 and will not be described again here.
Comparative example 2
The preparation of the negative electrode sheet is different from example 1:
weighing artificial graphite, sodium carboxymethyl cellulose and carboxyl styrene-butadiene rubber according to a mass ratio of 97.5:1.2:1.3, adding sodium carboxymethyl cellulose into deionized water to disperse into a glue solution, adding the artificial graphite and the carboxyl styrene-butadiene rubber into the glue solution, and stirring to obtain negative electrode slurry;
the remainder is the same as in example 1 and will not be described again here.
Comparative example 3
The positive electrode sheet was prepared differently from example 1:
weighing the doped and coated modified lithium cobaltate, polyvinylidene fluoride and carbon nano tubes prepared in the embodiment 1 according to the mass ratio of 97:1.5:1.5, adding the polyvinylidene fluoride into N-methyl pyrrolidone to be dispersed into uniform glue solution, adding the doped and coated modified lithium cobaltate and the carbon nano tubes into the glue solution, and stirring to prepare anode slurry;
the remainder is the same as in example 1 and will not be described again here.
Comparative example 4
The positive electrode sheet was prepared differently from example 1:
weighing the doped coated modified lithium cobaltate, polyvinylidene fluoride, carbon nano tube and polyvinylpyrrolidone prepared in the embodiment 1 according to the mass ratio of 97.35:1.0:0.65:1, adding the polyvinylidene fluoride into N-methyl pyrrolidone to be dispersed into uniform glue solution, adding the doped coated modified lithium cobaltate, the carbon nano tube and the polyvinylpyrrolidone into the glue solution, and stirring to prepare anode slurry;
the remainder is the same as in example 1 and will not be described again here.
Comparative example 5
The difference from example 1 is the preparation of positive and negative plates: the ratio of the capacity of the negative electrode active material per unit area to the capacity of the positive electrode active material per unit area is 1:1.
The remainder is the same as in example 1 and will not be described again here.
Comparative example 6
The difference from example 1 is the preparation of positive and negative plates: the ratio of the capacity of the negative electrode active material per unit area to the capacity of the positive electrode active material per unit area is 1.1:1.
The remainder is the same as in example 1 and will not be described again here.
The batteries prepared in examples 1 to 6 and comparative examples 1 to 6 were subjected to the following normal temperature cycle performance test, lithium precipitation test, low temperature performance test, hot box test:
(1) And (3) testing normal temperature cycle performance: charging to 4.48V (cut-off current is 0.05C) at 25deg.C under constant current and constant voltage, standing for 5min, discharging to 3.0V under constant current of 0.7C, and standing for 5min; cycling charge and discharge for 800 times; the 800 th discharge capacity is more than or equal to 80% of the initial capacity.
(2) 45 ℃ cycle performance test: charging to 4.48V (cut-off current is 0.05C) at 25deg.C under constant current and constant voltage, standing for 5min, discharging to 3.0V under constant current of 0.7C, and standing for 5min; cycling charge and discharge for 500 times; the 500 th discharge capacity is more than or equal to 80% of the initial capacity.
(3) Lithium precipitation test: charging the battery cell to 4.48V (cut-off current is 0.02C) at constant current and constant voltage of 2C at 25 ℃, standing for 5min, discharging the battery cell to 3.0V at constant current of 0.7C, and standing for 5min; and (5) cycling for 10 times, disassembling the battery core, wherein the occurrence of lithium precipitation is not passed the test, and the occurrence of lithium precipitation is not passed the test.
(4) Low temperature performance test: charging to 4.48V (cut-off current is 0.02C) at constant current and constant voltage of 0.5C at normal temperature, standing for 5min, discharging to 3.0V at constant current of 0.2C, and recording normal temperature discharge capacity 1; and (3) charging the formed battery to 4.48V (the cut-off current is 0.01C) at the constant current and constant voltage of 0.5C at the temperature of 20 ℃ below zero, discharging to 3.0V by using the constant current of 0.5C, and calculating the retention rate of 600-week cycle capacity of charge/discharge, wherein the retention rate of the cycle capacity is higher than 80 percent.
(5) Thermal shock test: the battery is fully charged according to a standard method, then is put into a temperature control box, the temperature of the box body is raised at (5+/-2) DEG C/min, and the temperature is kept for 60min after the temperature reaches 130 ℃; the battery should not fire or explode within 60 min.
The test results of examples 1 to 6 and comparative examples 1 to 6 are shown in Table 1.
TABLE 1
As can be seen from example 1 and comparative example 1, the cycle performance of comparative example 1 is significantly lower than that of example 1, because the lithium cobaltate of comparative example 1 is excessively delithiated after the charging voltage of the battery is raised from 4.40V to 4.48V, and the charge imbalance in the highly delithiated state causes expansion and shrinkage of the crystal structure of lithium cobaltate, resulting in occurrence of unit cells and dislocation, resulting in a decrease in the stability of the crystal structure of lithium cobaltate, and a substantial decrease in the cycle performance. The doped coated modified lithium cobaltate prepared in the embodiment 1 can avoid excessive lithium removal of the lithium cobaltate, reduce the oxidability of the lithium cobaltate and improve the structural stability of the lithium cobaltate crystal.
As can be seen from example 1 and comparative example 2, the use of carbon-coated graphite for the negative electrode can significantly improve the quick charge performance of the battery, mainly because the carbon-coated graphite negative electrode material can be applied to a quick charge type lithium cobaltate/graphite battery, is favorable for rapid diffusion of lithium ions and full intercalation into the lattice of the carbon-coated graphite, does not cause precipitation of lithium, and meets the requirement of high-current quick charge.
As can be seen from example 1 and comparative example 3, comparative example 3 does not add the polyvinylpyrrolidone as an anode prefilming additive, and the anode surface is fully contacted with the electrolyte to undergo oxidation-reduction reaction, so that the oxidation of the 4-valent cobalt to the electrolyte is increased, the electrolyte is decomposed and consumed, and the cycle performance of the battery is affected.
As can be seen from example 1 and comparative example 4, the excessive content of the positive electrode prefilming additive added in comparative example 4 reduces the contact of the positive electrode surface with the electrolyte to a greater extent, affects the migration rate of lithium ions, and reduces the gram capacity exertion of lithium cobaltate.
As can be seen from example 1 and comparative examples 5 to 6, the ratio of the coating amount of the negative electrode slurry per unit area to the coating amount of the positive electrode slurry per unit area needs to be controlled within a certain range, the ratio is too small, and lithium precipitation easily occurs in the battery cell; the ratio is too large, and the cycle performance of the battery cell is reduced.
In conclusion, the invention optimally designs the whole high-voltage lithium cobaltate/graphite battery system, wherein the anode adopts doped coating modified lithium cobaltate, so that the oxidability of the surface of the lithium cobaltate can be reduced, the structural stability of the lithium cobaltate is improved, the charge cut-off voltage is increased from 4.40V to 4.48V, the gram capacity is increased from 172mAh/g to 185mAh/g, and the platform voltage is increased from 3.83V to 3.88V; the anode prefilming additive is attached to the surface of the doped and coated modified lithium cobaltate particles along with the conductive agent, so that the contact between the anode surface and the electrolyte is reduced, and the oxidation of the 4-valent cobalt to the electrolyte is prevented to a certain extent. The cathode adopts carbon coated graphite, so that the quick charge function of the high-voltage lithium cobaltate/graphite battery is met, the electrochemical performance is good, the formula of the electrolyte is improved, and the electrolyte and an electrode interface are more stable. The high-voltage lithium cobaltate/graphite battery prepared by the method has the advantages of high energy density, good cycle performance, high safety performance, and quick charge and low-temperature charge capability.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (8)
1. A high voltage lithium cobaltate/graphite battery characterized by: the lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte;
the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, wherein the positive active material layer comprises a positive active material, a conductive agent, a positive binder and a positive pre-film-forming additive, the positive active material is doped and coated with modified lithium cobaltate, and the positive pre-film-forming additive is polyvinylpyrrolidone;
the negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer coated on the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material, a negative electrode binder and a dispersing agent, and the negative electrode active material is carbon-coated graphite;
the charge cut-off voltage of the high-voltage lithium cobaltate/graphite battery is 4.48V;
the ratio of the capacity of the negative electrode active material per unit area to the capacity of the positive electrode active material per unit area is (1.025-1.075): 1;
the preparation method of the doped coated modified lithium cobaltate comprises the following steps:
dissolving first cobalt salt and aluminum salt in deionized water, and carrying out coprecipitation reaction and heat treatment to obtain aluminum-doped first cobaltosic oxide particles;
dissolving second cobalt salt and aluminum salt in deionized water, and carrying out coprecipitation reaction and heat treatment to obtain aluminum-doped second cobaltosic oxide particles;
mixing a lithium source, the first cobaltosic oxide particles and a first additive, and performing ball milling, calcination, crushing and sieving to obtain first coated lithium cobaltate particles;
mixing a lithium source, the second cobaltosic oxide particles and the first additive, and performing ball milling, calcination, crushing and sieving to obtain first coated second lithium cobaltate particles;
mixing the first lithium cobaltate particles, the second lithium cobaltate particles and the second additive for secondary coating, and performing ball milling, calcination, crushing and sieving to obtain the doped coated modified lithium cobaltate.
2. The high voltage lithium cobaltate/graphite cell of claim 1 wherein,
the median particle size of the first cobaltosic oxide particles is greater than the median particle size of the second cobaltosic oxide particles; the median particle size of the first lithium cobaltate particles is greater than the median particle size of the second lithium cobaltate particles.
3. The high voltage lithium cobaltate/graphite cell of claim 2 wherein the lithium source comprises at least one of lithium carbonate, lithium hydroxide, and lithium oxalate; the first additive comprises at least one element of Mg, al, ti or Zr; the second additive is a compound containing at least one element of Mg, al, ti or Zr.
4. The high voltage lithium cobaltate/graphite cell of claim 1 wherein the mass ratio of the positive electrode active material, the positive electrode binder, the conductive agent and the positive electrode prefilming additive is 96-99:0.8-2:0.03-0.2.
5. The high-voltage lithium cobaltate/graphite battery according to claim 1, wherein the mass ratio of the negative electrode active material, the negative electrode binder and the dispersant is 97-98.5:0.8-1.5:0.7-1.5.
6. The high voltage lithium cobaltate/graphite cell of claim 1 wherein the dispersant is sodium carboxymethyl cellulose.
7. The high voltage lithium cobaltate/graphite cell of claim 1 wherein the carbon coated graphite has a median particle diameter D50 of 12 to 23 μm, a specific surface area of 1.0 to 2.0 square meter/g, and a graphitization degree of 93.0 to 94.0%.
8. A method of manufacturing a high voltage lithium cobaltate/graphite cell according to any one of claims 1 to 7 comprising the steps of:
firstly, weighing doped coated modified lithium cobaltate, a positive electrode binder, a conductive agent and a positive electrode prefilming additive, adding the positive electrode binder into N-methyl pyrrolidone, dispersing into uniform first glue solution, adding the doped coated modified lithium cobaltate, the conductive agent and the positive electrode prefilming additive into the first glue solution, and stirring to obtain positive electrode slurry; weighing carbon-coated graphite, a dispersing agent and a negative electrode binder, adding the dispersing agent into deionized water to be dispersed into a second glue solution, adding the carbon-coated graphite and the negative electrode binder into the second glue solution, and stirring to obtain a negative electrode slurry;
step two, uniformly coating the positive electrode slurry and the negative electrode slurry on a positive electrode current collector and a negative electrode current collector respectively, and rolling, slitting, welding a tab and rubberizing to obtain a positive electrode plate and a negative electrode plate;
and thirdly, laminating and/or winding the positive plate, the negative plate and the diaphragm to prepare a winding core, packaging, vacuum baking, injecting electrolyte, standing, high-temperature high-pressure formation, degassing, packaging and capacity division to obtain the high-voltage lithium cobalt oxide/graphite battery.
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| CN111599995A (en) * | 2020-04-28 | 2020-08-28 | 惠州锂威新能源科技有限公司 | Cathode material, preparation method thereof and high-voltage lithium ion battery |
| CN111525089B (en) * | 2020-07-06 | 2020-11-10 | 长沙宝锋能源科技有限公司 | Low-temperature lithium ion battery with energy density and safety |
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| CN114212833B (en) * | 2021-11-24 | 2024-05-24 | 惠州锂威新能源科技有限公司 | Modified lithium cobalt oxide positive electrode material, preparation method thereof, positive electrode plate and secondary battery |
| CN114212785A (en) * | 2021-11-26 | 2022-03-22 | 惠州锂威新能源科技有限公司 | Negative electrode material and preparation method thereof, negative plate and lithium ion battery |
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