CN103107309A - Lithium ion battery positive pole and preparation method thereof - Google Patents
Lithium ion battery positive pole and preparation method thereof Download PDFInfo
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- CN103107309A CN103107309A CN2013100388046A CN201310038804A CN103107309A CN 103107309 A CN103107309 A CN 103107309A CN 2013100388046 A CN2013100388046 A CN 2013100388046A CN 201310038804 A CN201310038804 A CN 201310038804A CN 103107309 A CN103107309 A CN 103107309A
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Abstract
The invention provides a preparation method of a lithium ion battery positive pole. The preparation method comprises the following steps of: mixing a precursor of a lithium ion battery positive pole material, a bonding agent and a dispersing agent to prepare a sizing agent, wherein the precursor of the lithium ion battery positive pole material is a ferric phosphate lithium precursor or a phosphoric acid vanadium lithium precursor; coating the sizing agent on a non-woven fabric type film, and drying to obtain the precursor of the lithium ion battery positive pole; and sintering the precursor of the lithium ion battery positive pole under the condition of protective gas to obtain the lithium ion battery positive pole. The lithium ion battery prepared from the lithium ion battery positive pole provided by the invention high loading capacity, and good multiplying power performance and cycle performance.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion cell positive and preparation method thereof.
Background technology
Since Sony company in 1991 releases the commodity lithium ion battery first, through the development of 20 years, lithium ion battery high with its open circuit voltage, have extended cycle life, energy density is high, self discharge is low, memory-less effect, the advantage such as environmentally friendly are widely used in people's work, study, life various aspects.
In recent years, along with the market demand of electrokinetic cell and large-scale power energy storage device constantly increases, occurred successively with power and the accumulation power supply of lithium ion battery as carrier.As electrical source of power, lithium ion battery need to be realized the high characteristic of charge/discharge capacity under large multiplying power.And the positive pole of lithium ion battery is the key factor that affects performance of lithium ion battery.
The positive electrode that the positive pole of lithium ion battery comprises plus plate current-collecting body and is formed at this anode collection surface.Plus plate current-collecting body in lithium ion cell positive is the structure of collecting electric current, the effect of plus plate current-collecting body is mainly that the electric current that cell positive material produces is collected, so that forming larger electric current externally exports, therefore, plus plate current-collecting body should fully contact with positive electrode, and internal resistance is as far as possible little.The plus plate current-collecting body of lithium ion battery is generally sheet metal, as Copper Foil, aluminium foil.In the prior art, the preparation method of lithium ion cell positive is: positive electrode is prepared into slurry, is coated on sheet metal, can obtain lithium ion cell positive after drying.But lower, the high rate performance of discharge capacity of lithium ion battery and the cycle performance of preparation are relatively poor take above-mentioned lithium ion cell positive as raw material.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of lithium ion cell positive and preparation method thereof, and the lithium ion cell positive that the present invention is prepared is applied in lithium ion battery, and discharge capacity is high, high rate performance and good cycle.
The invention provides a kind of preparation method of lithium ion cell positive, comprise the following steps:
A) with precursor of lithium ionic cell positive material, binding agent and dispersant, make slurry;
Described precursor of lithium ionic cell positive material is ferric lithium phosphate precursor or phosphoric acid vanadium lithium presoma;
B) described slurry is coated on the non-woven fabric type film, obtains the lithium ion cell positive presoma after drying;
C) under the condition of protective gas, described lithium ion cell positive presoma is carried out sintering, obtain lithium ion cell positive.
Preferably, described non-woven fabric type film is one or more in polypropylene fibre, terylene, polyamide fibre, viscose rayon, acrylic fibers, polyethylene and paper.
Preferably, described binding agent is one or more in Kynoar, polytetrafluoroethylene, sodium carboxymethylcellulose and butadiene-styrene rubber.
Preferably, described dispersant be in 1-Methyl-2-Pyrrolidone, ethanol, distilled water, deionized water and acetone one or more.
Preferably, described protective gas is one or more in argon gas, nitrogen and helium.
Preferably, the temperature of described sintering is 550 ~ 900 ℃, and the time of sintering is 2 ~ 20h.
Preferably, the mass ratio of described precursor of lithium ionic cell positive material, binding agent and dispersant is (5 ~ 10): (1 ~ 5): (10 ~ 15).
Preferably, described ferric lithium phosphate precursor is prepared as follows: after lithium source, source of iron, phosphorus source, carbon source and solvent, ball milling, drying, calcining, obtain ferric lithium phosphate precursor;
Described phosphoric acid vanadium lithium presoma is prepared as follows: after lithium source, vanadium source, phosphorus source, carbon source and solvent, ball milling, drying, calcining, obtain the phosphoric acid vanadium lithium presoma.
Preferably, described lithium source be in lithium carbonate, lithium dihydrogen phosphate, lithium acetate, lithium nitrate and lithium hydroxide one or more;
Described source of iron be in ferrous oxalate, ferrous acetate, ferric oxalate, ferric acetate, ferric nitrate, ferric phosphate, di-iron trioxide, tri-iron tetroxide and ferrous oxide one or more;
Described vanadium source be in vanadic oxide, vanadium trioxide, vanadium dioxide and ammonium metavanadate one or more;
Described phosphorus source is one or more in ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ferric phosphate;
Described carbon source is lignocellulosic;
Described solvent be in deionized water, distilled water, industrial alcohol, absolute ethyl alcohol and acetone one or more.
The present invention also provides a kind of lithium ion cell positive by preparation method's preparation provided by the present invention.
Compared with prior art, the present invention makes slurry with precursor of lithium ionic cell positive material, binding agent and dispersant; Described slurry is coated on the non-woven fabric type film, obtains the lithium ion cell positive presoma after drying; Under the condition of protective gas, described lithium ion cell positive presoma is carried out sintering, obtain lithium ion cell positive; Described precursor of lithium ionic cell positive material is ferric lithium phosphate precursor or phosphoric acid vanadium lithium presoma.The present invention is take the non-woven fabric type film as raw material, by step heat treatment altogether, non-woven fabric type film in-situ carburization forms plus plate current-collecting body, described plus plate current-collecting body has three-dimensional porous structure, increased the contact area between plus plate current-collecting body and positive electrode, reduce contact resistance, improved electronic conductivity, the discharge capacity of lithium ion battery for preparing is high, high rate performance and good cycle.In addition, the battery plus plate current-collecting body of preparation, reduced the lithium ion battery cost take the non-woven fabric type film as raw material.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the lithium ion cell positive section of the embodiment of the present invention 1 preparation;
Fig. 2 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 1 ~ 4 preparation;
Fig. 3 is the electrode high rate performance figure of the half-cell of the embodiment of the present invention 5 preparations;
Fig. 4 is the electrode high rate performance figure of the half-cell of Comparative Examples 1 preparation of the present invention;
Fig. 5 is the half-cell of the embodiment of the present invention 5 preparations and the cycle performance comparison diagram of the half-cell that Comparative Examples 1 prepares;
Fig. 6 is the scanning electron microscope (SEM) photograph of the lithium ion cell positive section of the embodiment of the present invention 6 preparations;
Fig. 7 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 6 ~ 9 preparations;
Fig. 8 is the electrode high rate performance figure of the half-cell of the embodiment of the present invention 10 preparations;
Fig. 9 is the electrode high rate performance figure of the half-cell of Comparative Examples 2 preparations of the present invention;
Figure 10 is the cycle performance figure of the half-cell of the embodiment of the present invention 10 preparations.
Embodiment
The invention provides a kind of preparation method of lithium ion cell positive, comprise the following steps:
A) with precursor of lithium ionic cell positive material, binding agent and dispersant, make slurry;
Described precursor of lithium ionic cell positive material is ferric lithium phosphate precursor or phosphoric acid vanadium lithium presoma;
B) described slurry is coated on the non-woven fabric type film, obtains the lithium ion cell positive presoma after drying;
C) under the condition of protective gas, described lithium ion cell positive presoma is carried out sintering, obtain lithium ion cell positive.
At first the present invention with precursor of lithium ionic cell positive material, binding agent and dispersant, makes slurry, and described precursor of lithium ionic cell positive material is ferric lithium phosphate precursor or phosphoric acid vanadium lithium presoma.
The present invention does not have particular restriction to the source of described ferric lithium phosphate precursor or phosphoric acid vanadium lithium presoma, can be according to method preparation well known to those skilled in the art, in the present invention, described ferric lithium phosphate precursor preferably is prepared as follows: after lithium source, source of iron, phosphorus source, carbon source and solvent, ball milling, drying, calcining, obtain ferric lithium phosphate precursor.At first the present invention mixes lithium source, source of iron, phosphorus source and carbon source, there is no particular restriction for described hybrid mode, can be mechanical mixture, mixes etc.Mixed lithium source, source of iron, phosphorus source and carbon source are carried out ball milling, obtain mixed liquor, described ball milling is ball milling well known to those skilled in the art, the present invention preferably adopts wet ball grinding, wherein solvent is that dispersant is preferably in deionized water, distilled water, industrial alcohol, absolute ethyl alcohol and acetone one or more, more preferably acetone.Mixed liquor after wet ball grinding is carried out drying in air, calcine under inert gas conditions again through grinding after drying, obtain ferric lithium phosphate precursor.Wherein, the temperature of described drying is preferably 30 ~ 120 ℃, more preferably 50 ~ 100 ℃; The dry time is preferably 1 ~ 48h, more preferably 2 ~ 40h.Described inert gas is preferably one or more in argon gas, nitrogen and helium, more preferably nitrogen.The temperature of described calcining is preferably 200 ~ 500 ℃, more preferably 250 ~ 450 ℃; The time of described calcining is 2 ~ 20h, more preferably 5 ~ 15h.In the present invention, described lithium source is preferably in lithium carbonate, lithium dihydrogen phosphate, lithium acetate, lithium nitrate and lithium hydroxide one or more, more preferably lithium carbonate; Described source of iron is preferably in ferrous oxalate, ferrous acetate, ferric oxalate, ferric acetate, ferric nitrate, ferric phosphate, di-iron trioxide, tri-iron tetroxide and ferrous oxide one or more, more preferably one or more in ferrous oxalate or iron oxide; Described phosphorus source is preferably one or more in ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ferric phosphate, more preferably ammonium dihydrogen phosphate; Described carbon source is preferably lignocellulosic, and described lignocellulosic is selected from and includes but not limited to one or more in trees sawdust, maize straw, hemp stalk, straw, straw, bagasse, Original Pulp, stationery and cotton.In described lithium source, source of iron, phosphorus source, the mol ratio of lithium, iron, P elements is (1 ~ 2): (1 ~ 2): (1 ~ 2), more preferably (1.2 ~ 1.8): (1.2 ~ 1.8): (1.2 ~ 1.8).The quality of described lignocellulosic is preferably (0.05 ~ 0.35) with the ratio of the quality of theoretical LiFePO4: 1, more preferably (0.10 ~ 0.30): 1, the quality of the LiFePO4 that the quality of described theoretical LiFePO4 calculates for the addition according to described lithium source, source of iron and phosphorus source.The quality that finally obtains LiFePO4 is the quality of actual LiFePO4, and in the LiFePO4 that wherein finally obtains, the content of carbon is preferably 0.01wt% ~ 20wt%, more preferably 1wt% ~ 18wt%.
Phosphoric acid vanadium lithium presoma of the present invention preferably is prepared as follows: after lithium source, vanadium source, phosphorus source, carbon source and solvent, ball milling, drying, calcining, obtain the phosphoric acid vanadium lithium presoma.At first the present invention mixes lithium source, vanadium source, phosphorus source and carbon source, there is no particular restriction for described hybrid mode, can be mechanical mixture, mixes etc.Mixed lithium source, vanadium source, phosphorus source and carbon source are carried out ball milling, obtain mixed liquor, described ball milling is ball milling well known to those skilled in the art, the present invention preferably adopts wet ball grinding, wherein said solvent is that dispersant is preferably in deionized water, distilled water, industrial alcohol, absolute ethyl alcohol and acetone one or more, more preferably acetone.Mixed liquor after wet ball grinding is carried out drying in air, calcine under inert gas conditions again through grinding after drying, obtain the phosphoric acid vanadium lithium presoma.Wherein, the temperature of described drying is preferably 30 ~ 120 ℃, more preferably 50 ~ 100 ℃; The dry time is preferably 1 ~ 48h, more preferably 2 ~ 40h.Described inert gas is preferably one or more in argon gas, nitrogen and helium, more preferably nitrogen.The temperature of described calcining is preferably 200 ~ 500 ℃, more preferably 250 ~ 450 ℃; The time of described calcining is 2 ~ 20h, more preferably 5 ~ 15h.In the present invention, described lithium source is preferably in lithium carbonate, lithium dihydrogen phosphate, lithium acetate, lithium nitrate and lithium hydroxide one or more, more preferably lithium carbonate; Described vanadium source is preferably in vanadic oxide, vanadium trioxide, vanadium dioxide and ammonium metavanadate one or more, more preferably ammonium metavanadate and vanadium dioxide; Described phosphorus source is preferably one or more in ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ferric phosphate, more preferably ammonium dihydrogen phosphate; Described carbon source is preferably lignocellulosic, and described lignocellulosic is selected from and includes but not limited to one or more in trees sawdust, maize straw, hemp stalk, straw, straw, bagasse, Original Pulp, stationery and cotton.In described lithium source, vanadium source, phosphorus source, the mol ratio of lithium, vanadium, P elements is (3 ~ 4): (2 ~ 3): (3 ~ 4), more preferably (3.2 ~ 3.8): (2.2 ~ 2.8): (3.2 ~ 3.8).The quality of described lignocellulosic is preferably (0.05 ~ 0.35) with the ratio of the quality of theoretical phosphoric acid vanadium lithium: 1, more preferably (0.10 ~ 0.30): 1, the quality of the phosphoric acid vanadium lithium that the quality of described theoretical phosphoric acid vanadium lithium calculates for the addition according to described lithium source, vanadium source and phosphorus source.The quality that finally obtains phosphoric acid vanadium lithium is the quality of actual phosphoric acid vanadium lithium, and in the phosphoric acid vanadium lithium that wherein finally obtains, the content of carbon is preferably 0.01wt% ~ 20wt%, more preferably 1wt% ~ 18wt%.
With the above-mentioned precursor of lithium ionic cell positive material for preparing, binding agent and dispersant, make slurry.Described binding agent is preferably one or more in Kynoar, polytetrafluoroethylene, sodium carboxymethylcellulose and butadiene-styrene rubber, more preferably Kynoar; Described dispersant be in 1-Methyl-2-Pyrrolidone, ethanol, distilled water, deionized water and acetone one or more, 1-Methyl-2-Pyrrolidone more preferably.In the present invention, addition to described dispersant there is no particular restriction, wetting the getting final product of mixture with described positive electrode presoma and binding agent, the mass ratio of described precursor of lithium ionic cell positive material, binding agent and dispersant is preferably (5 ~ 10): (1 ~ 5): (10 ~ 15), more preferably (7 ~ 9): (1.5 ~ 2): (12 ~ 14).The present invention does not have particular restriction to described hybrid mode, and hybrid mode well known to those skilled in the art gets final product, and can be mechanical mixture, can be for mixing yet.
The present invention is coated on described slurry on the non-woven fabric type film, obtains the lithium ion cell positive presoma after drying.The present invention does not have particular restriction for described coating method, and coating method well known to those skilled in the art gets final product.Described non-woven fabric type film is preferably one or more in polypropylene fibre, terylene, polyamide fibre, viscose rayon, acrylic fibers, polyethylene and paper, polypropylene fibre more preferably, one or more in terylene, acrylic fibers and rice paper.The present invention there is no particular restriction to the source of described non-woven fabric type film, can be for generally commercially available.The thickness of described non-woven fabric type film is preferably 10 ~ 1000 μ m, more preferably 100 ~ 500 μ m.The present invention does not have particular restriction for described drying mode, can carry out drying in baking oven, and the temperature of described drying is preferably 80 ~ 120 ℃, more preferably 90 ~ 100 ℃; The time of described drying is preferably 2 ~ 20h, more preferably 5 ~ 15h.
The lithium ion cell positive presoma that obtains is placed in protective gas carries out sintering, obtain lithium ion cell positive.In the present invention, described protective gas is preferably one or more in argon gas, nitrogen and helium, more preferably nitrogen.The temperature of described sintering is preferably 550 ~ 900 ℃, more preferably 600 ~ 800 ℃; The time of described sintering is preferably 2 ~ 20h, more preferably 5 ~ 15h.Wherein, precursor of lithium ionic cell positive material obtains anode material for lithium-ion batteries after high temperature sintering, and namely ferric lithium phosphate precursor is through obtaining LiFePO4 or the phosphoric acid vanadium lithium presoma obtains phosphoric acid vanadium lithium after oversintering after oversintering; The non-woven fabric type film is at high temperature after sintering, in-situ carburization obtains the lithium ion cell positive collector, described lithium ion cell positive collector has three-dimensional porous structure, increased the contact area between lithium ion cell positive collector and positive electrode, reduce contact resistance, improved electronic conductivity.In addition, the non-woven fabric type film is cheap, and the battery plus plate current-collecting body of preparation take the non-woven fabric type film as raw material can reduce the cost of lithium ion battery.
The present invention also provides a kind of lithium ion cell positive that is prepared by preparation method provided by the present invention.
With the positive pole of the prepared lithium ion cell positive of the present invention as battery, with the negative pole of lithium sheet as battery, prepare half-cell, measure the chemical property of described half-cell under the condition of 25 ℃.Result shows, the lithium ion cell positive that the present invention is prepared is compared with the lithium ion cell positive take aluminium foil as collector, and discharge capacity is high, high rate performance and good cycle.
In order further to understand the present invention, below in conjunction with embodiment, lithium ion cell positive provided by the invention and preparation method thereof is described, protection scope of the present invention is not limited by the following examples.
0.025mol lithium carbonate, 0.05mol ferrous oxalate, 0.05mol ammonium dihydrogen phosphate, 1.5g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the lithium iron phosphate positive material presoma.
The above-mentioned lithium iron phosphate positive material presoma of 6g is modulated into slurry with 0.65g Kynoar and 12g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the polypropylene fibre that thickness is 100 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 630 ℃ of insulation 5h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
Section to the lithium ion cell positive that obtains carries out the Electronic Speculum surface sweeping, the results are shown in Figure 1, Fig. 1 is the scanning electron microscope (SEM) photograph of the lithium ion cell positive section of the embodiment of the present invention 1 preparation, wherein, 1 is lithium ion battery anode material lithium iron phosphate, and 2 is the lithium ion cell positive collector.As shown in Figure 1, in the lithium ion cell positive that embodiment 1 prepares, plus plate current-collecting body is three-dimensional porous structure, and in the most of three-dimensional porous structure that embeds plus plate current-collecting body of lithium ion battery anode material lithium iron phosphate, and with the plus plate current-collecting body close contact.
The lithium ion cell positive that obtains is carried out X-ray diffraction, and the results are shown in Figure 2, Fig. 2 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 1 ~ 4 preparation, and wherein 1 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 1 preparation.As shown in Figure 2, the lithium ion cell positive of the embodiment of the present invention 1 preparation is the LiFePO4 of pure phase olivine-type structure, without obviously crystalline phase impurity existence.
The lithium ion cell positive that obtains with embodiment 1 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains with the different discharge-rate of 0.2C, 1C, 2C and 5C, the results are shown in Table 1, table 1 is the normalization discharge capacity of half-cell under different discharge-rates of embodiment 1 ~ 4 preparation.Wherein, take the high discharge capacity of 0.2C as standard value, namely take the high discharge capacity of 0.2C as 1.
0.025mol lithium carbonate, 0.05mol ferrous oxalate, 0.05mol ammonium dihydrogen phosphate, 1.5g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the lithium iron phosphate positive material presoma.
The above-mentioned lithium iron phosphate positive material presoma of 6g is modulated into slurry with 0.65g Kynoar and 12g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the polypropylene fibre that thickness is 100 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 630 ℃ of insulation 8h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
The lithium ion cell positive that obtains is carried out X-ray diffraction, and the results are shown in Figure 2, Fig. 2 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 1 ~ 4 preparation, and wherein 2 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 2 preparations.As shown in Figure 2, the lithium ion cell positive of the embodiment of the present invention 2 preparations is the LiFePO4 of pure phase olivine-type structure, without obviously crystalline phase impurity existence.
The lithium ion cell positive that obtains with embodiment 2 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains with the different discharge-rate of 0.2C, 1C, 2C and 5C, the results are shown in Table 1, table 1 is the normalization discharge capacity of half-cell under different discharge-rates of embodiment 1 ~ 4 preparation.Wherein, take the high discharge capacity of 0.2C as standard value, namely take the high discharge capacity of 0.2C as 1.
0.025mol lithium carbonate, 0.05mol ferrous oxalate, 0.05mol ammonium dihydrogen phosphate, 1.5g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the lithium iron phosphate positive material presoma.
The above-mentioned lithium iron phosphate positive material presoma of 6g is modulated into slurry with 0.65g Kynoar and 12g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the terylene that thickness is 100 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 660 ℃ of insulation 5h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
The lithium ion cell positive that obtains is carried out X-ray diffraction, and the results are shown in Figure 2, Fig. 2 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 1 ~ 4 preparation, and wherein 3 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 3 preparations.As shown in Figure 2, the lithium ion cell positive of the embodiment of the present invention 3 preparations is the LiFePO4 of pure phase olivine-type structure, without obviously crystalline phase impurity existence.
The lithium ion cell positive that obtains with embodiment 3 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains with the different discharge-rate of 0.2C, 1C, 2C and 5C, the results are shown in Table 1, table 1 is the normalization discharge capacity of half-cell under different discharge-rates of embodiment 1 ~ 4 preparation.Wherein, take the high discharge capacity of 0.2C as standard value, namely take the high discharge capacity of 0.2C as 1.
0.025mol lithium carbonate, 0.05mol ferrous oxalate, 0.05mol ammonium dihydrogen phosphate, 1.5g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the lithium iron phosphate positive material presoma.
The above-mentioned lithium iron phosphate positive material presoma of 6g is modulated into slurry with 0.65g Kynoar and 12g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the terylene of 200 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 660 ℃ of insulation 8h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
The lithium ion cell positive that obtains is carried out X-ray diffraction, and the results are shown in Figure 2, Fig. 2 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 1 ~ 4 preparation, and wherein 4 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 4 preparations.As shown in Figure 2, the lithium ion cell positive of the embodiment of the present invention 4 preparations is the LiFePO4 of pure phase olivine-type structure, without obviously crystalline phase impurity existence.
The lithium ion cell positive that obtains with embodiment 4 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains with the different discharge-rate of 0.2C, 1C, 2C and 5C, the results are shown in Table 1, table 1 is the normalization discharge capacity of half-cell under different discharge-rates of embodiment 1 ~ 4 preparation.Wherein, take the high discharge capacity of 0.2C as standard value, namely take the high discharge capacity of 0.2C as 1.
The normalization discharge capacity of half-cell under different discharge-rates of table 1 embodiment 1 ~ 4 preparation
As shown in Table 1, the prepared lithium ion cell positive of the present invention has high rate performance preferably, and capability retention is higher under high magnification.
0.025mol lithium carbonate, 0.025mol iron oxide, 0.05mol ammonium dihydrogen phosphate, 1.5g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the lithium iron phosphate positive material presoma.
The above-mentioned lithium iron phosphate positive material presoma of 6g is modulated into slurry with 0.65g Kynoar and 12g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the rice paper of 100 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 660 ℃ of insulation 5h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
The lithium ion cell positive that obtains with embodiment 5 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains when 0.2C, 1C, 2C and 5C multiplying power, the results are shown in Figure 3, Fig. 3 is the electrode high rate performance figure of the half-cell of the embodiment of the present invention 5 preparations.Take the high discharge capacity of 0.2C as 1, in Fig. 3,1 is the normalization discharge capacity of half-cell when 0.2C of embodiment 5 preparations, 2 is the normalization discharge capacity of half-cell when 1C of embodiment 5 preparations, 3 is the normalization discharge capacity of half-cell when 2C of embodiment 5 preparations, and 4 is the normalization discharge capacity of half-cell when 5C of embodiment 5 preparations.
Under 25 ℃, with the half-cell that makes discharge cycles 14 ~ 20 times under the multiplying power of discharge cycles under the multiplying power of discharge cycles 4 ~ 8 times, 2C under the multiplying power of discharge cycles under the multiplying power of 0.2C 1 ~ 3 time, 1C 9 ~ 13 times and 5C respectively, measure the cycle performance of the half-cell of embodiment 5 preparations.The results are shown in Figure 5, Fig. 5 is the half-cell of the embodiment of the present invention 5 preparations and the cycle performance comparison diagram of the half-cell that Comparative Examples 1 prepares.Wherein, 1 is the cycle performance curve of the half-cell of the embodiment of the present invention 5 preparations.
Comparative Examples 1
0.025mol lithium carbonate, 0.025mol iron oxide, 0.05mol ammonium dihydrogen phosphate, 1.5g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the lithium iron phosphate positive material presoma.
Described lithium iron phosphate positive material presoma is carried out sintering with 660 ℃ of insulation 5h under the protection of nitrogen, the product after sintering is lithium iron phosphate positive material.Above-mentioned lithium iron phosphate positive material, 0.57g Kynoar, 0.57g acetylene black and the 12g1-N-methyl-2-2-pyrrolidone N-of 6g after fully grinding is modulated into slurry, described slurry is coated on aluminium foil, dry 2h, obtain lithium ion cell positive under 120 ℃.
The lithium ion cell positive that obtains with Comparative Examples 1 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains when 0.2C, 1C, 2C and 5C multiplying power, the results are shown in Figure 4, Fig. 4 is the electrode high rate performance figure of the half-cell of Comparative Examples 1 preparation of the present invention.Take the high discharge capacity of 0.2C as 1, in Fig. 4,1 is the normalization discharge capacity of half-cell when 0.2C of Comparative Examples 1 preparation, 2 is the normalization discharge capacity of half-cell when 1C of Comparative Examples 1 preparation, 3 is the normalization discharge capacity of half-cell when 2C of Comparative Examples 1 preparation, and 4 is the normalization discharge capacity of half-cell when 5C of Comparative Examples 1 preparation.
By Fig. 3 and Fig. 4 as can be known, compare with the half-cell of Comparative Examples 1 preparation, the discharge-rate performance is good first for the prepared half-cell of the embodiment of the present invention 5, and discharge first normalization capacity and discharge platform are all high.
Under 25 ℃, with the half-cell that makes discharge cycles 14 ~ 20 times under the multiplying power of discharge cycles under the multiplying power of discharge cycles 4 ~ 8 times, 2C under the multiplying power of discharge cycles under the multiplying power of 0.2C 1 ~ 3 time, 1C 9 ~ 13 times and 5C respectively, measure the cycle performance of the half-cell of embodiment 5 preparations.The results are shown in Figure 5, Fig. 5 is the half-cell of the embodiment of the present invention 5 preparations and the cycle performance comparison diagram of the half-cell that Comparative Examples 1 prepares.Wherein, 2 is the cycle performance curve of the half-cell of Comparative Examples 1 preparation of the present invention.
As shown in Figure 5, compare with the half-cell of Comparative Examples 1 preparation, the cycle performance of the half-cell of the embodiment of the present invention 5 preparations is better.
Embodiment 6
0.0375mol lithium carbonate, 0.05mol ammonium metavanadate, 0.075mol ammonium dihydrogen phosphate, 2g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the vanadium phosphate cathode material presoma.
The above-mentioned vanadium phosphate cathode material presoma of 18g is modulated into slurry with 2g Kynoar and 20g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the polypropylene fibre that thickness is 100 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 630 ℃ of insulation 5h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
Section to the lithium ion cell positive that obtains carries out the Electronic Speculum surface sweeping, the results are shown in Figure 6, Fig. 6 is the scanning electron microscope (SEM) photograph of the lithium ion cell positive section of the embodiment of the present invention 6 preparations, wherein, 1 is cathode material lithium vanadium phosphate of lithium ion battery, and 2 is the lithium ion cell positive collector.As shown in Figure 6, in the lithium ion cell positive that embodiment 6 prepares, plus plate current-collecting body is three-dimensional porous structure, and in the most of three-dimensional porous structure that embeds plus plate current-collecting body of cathode material lithium vanadium phosphate of lithium ion battery, and with the plus plate current-collecting body close contact.
The lithium ion cell positive that obtains is carried out X-ray diffraction, and the results are shown in Figure 7, Fig. 7 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 6 ~ 9 preparations, and wherein 1 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 6 preparations.As shown in Figure 7, the lithium ion cell positive of the embodiment of the present invention 6 preparations is the phosphoric acid vanadium lithium of pure phase olivine-type structure, without obviously crystalline phase impurity existence.
The lithium ion cell positive that obtains with embodiment 6 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains with the different discharge-rate of 0.1C, 0.25C, 0.5C, 1C and 1.5C, the results are shown in Table 2, table 2 is the normalization discharge capacity of half-cell under different discharge-rates of embodiment 6 ~ 9 preparations.Wherein, take the high discharge capacity of 0.1C as standard value, namely take the high discharge capacity of 0.1C as 1.
Embodiment 7
0.0375mol lithium carbonate, 0.05mol ammonium metavanadate, 0.075mol ammonium dihydrogen phosphate, 2g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the vanadium phosphate cathode material presoma.
The above-mentioned vanadium phosphate cathode material presoma of 18g is modulated into slurry with 2g Kynoar and 20g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the polypropylene fibre that thickness is 200 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 630 ℃ of insulation 8h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
The lithium ion cell positive that obtains is carried out X-ray diffraction, and the results are shown in Figure 7, Fig. 7 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 6 ~ 9 preparations, and wherein 2 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 7 preparations.As shown in Figure 7, the lithium ion cell positive of the embodiment of the present invention 7 preparations is the phosphoric acid vanadium lithium of pure phase olivine-type structure, without obviously crystalline phase impurity existence.
The lithium ion cell positive that obtains with embodiment 7 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains with the different discharge-rate of 0.1C, 0.25C, 0.5C, 1C and 1.5C, the results are shown in Table 2, table 2 is the normalization discharge capacity of half-cell under different discharge-rates of embodiment 6 ~ 9 preparations.Wherein, take the high discharge capacity of 0.1C as standard value, namely take the high discharge capacity of 0.1C as 1.
Embodiment 8
0.0375mol lithium carbonate, 0.05mol ammonium metavanadate, 0.075mol ammonium dihydrogen phosphate, 2g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the vanadium phosphate cathode material presoma.
The above-mentioned vanadium phosphate cathode material presoma of 18g is modulated into slurry with 2g Kynoar and 20g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the terylene that thickness is 100 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 660 ℃ of insulation 5h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
The lithium ion cell positive that obtains is carried out X-ray diffraction, and the results are shown in Figure 7, Fig. 7 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 6 ~ 9 preparations, and wherein 3 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 8 preparations.As shown in Figure 7, the lithium ion cell positive of the embodiment of the present invention 8 preparations is the phosphoric acid vanadium lithium of pure phase olivine-type structure, without obviously crystalline phase impurity existence.
The lithium ion cell positive that obtains with embodiment 8 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains with the different discharge-rate of 0.1C, 0.25C, 0.5C, 1C and 1.5C, the results are shown in Table 2, table 2 is the normalization discharge capacity of half-cell under different discharge-rates of embodiment 6 ~ 9 preparations.Wherein, take the high discharge capacity of 0.1C as standard value, namely take the high discharge capacity of 0.1C as 1.
0.0375mol lithium carbonate, 0.05mol ammonium metavanadate, 0.075mol ammonium dihydrogen phosphate, 2g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the vanadium phosphate cathode material presoma.
The above-mentioned vanadium phosphate cathode material presoma of 18g is modulated into slurry with 2g Kynoar and 20g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the terylene that thickness is 200 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 660 ℃ of insulation 8h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
The lithium ion cell positive that obtains is carried out X-ray diffraction, and the results are shown in Figure 7, Fig. 7 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 6 ~ 9 preparations, and wherein 4 is the XRD collection of illustrative plates of the lithium ion cell positive of the embodiment of the present invention 9 preparations.As shown in Figure 7, the lithium ion cell positive of the embodiment of the present invention 9 preparations is the phosphoric acid vanadium lithium of pure phase olivine-type structure, without obviously crystalline phase impurity existence.
The lithium ion cell positive that obtains with embodiment 9 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains with the different discharge-rate of 0.1C, 0.25C, 0.5C, 1C and 1.5C, the results are shown in Table 2, table 2 is the normalization discharge capacity of half-cell under different discharge-rates of embodiment 6 ~ 9 preparations.Wherein, take the high discharge capacity of 0.1C as standard value, namely take the high discharge capacity of 0.1C as 1.
The normalization discharge capacity of half-cell under different discharge-rates of table 2 embodiment 6 ~ 9 preparations
As shown in Table 2, the prepared lithium ion cell positive of the present invention has high rate performance preferably, and capability retention is higher under high magnification.
0.0375mol lithium carbonate, 0.025mol vanadium oxide, 0.075mol ammonium dihydrogen phosphate, 1.5g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the vanadium phosphate cathode material presoma.
The above-mentioned vanadium phosphate cathode material presoma of 18g is modulated into slurry with 2g Kynoar and 20g1-N-methyl-2-2-pyrrolidone N-after fully grinding, described slurry is coated on the rice paper that thickness is 100 μ m, dry 2h under 120 ℃ obtains the lithium ion cell positive presoma.Described lithium ion cell positive presoma is carried out sintering with 660 ℃ of insulation 8h under the protection of nitrogen, the product after sintering is lithium ion cell positive.
The lithium ion cell positive that obtains with embodiment 10 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains when 0.1C, 0.25C, 0.5C, 1C and 1.5C multiplying power, the results are shown in Figure 8, Fig. 8 is the electrode high rate performance figure of the half-cell of the embodiment of the present invention 10 preparations.Take the high discharge capacity of 0.1C as 1, in Fig. 8,1 is the normalization discharge capacity of half-cell when 0.1C of embodiment 10 preparations, 2 is the normalization discharge capacity of half-cell when 0.25C of embodiment 10 preparations, 3 is the normalization discharge capacity of half-cell when 0.5C of embodiment 10 preparations, 4 is the normalization discharge capacity of half-cell when 1C of embodiment 10 preparations, and 5 is the normalization discharge capacity of half-cell when 1.5C of embodiment 10 preparations.
Under 25 ℃, with the half-cell that makes discharge cycles 19 ~ 95 times under the multiplying power of discharge cycles 14 ~ 18 times and 1.5C under discharge cycles 9 ~ 13 times under discharge cycles 4 ~ 8 times under discharge cycles under the multiplying power of 0.1C 1 ~ 3 time, multiplying power at 0.25C, multiplying power at 0.5C, multiplying power at 1C respectively, measure the cycle performance of the half-cell of embodiment 10 preparations.The results are shown in Figure 10, Figure 10 is the cycle performance figure of the half-cell of the embodiment of the present invention 10 preparations.As shown in Figure 10, the cycle performance of the prepared half-cell of the present invention is better.
Comparative Examples 2
0.0375mol lithium carbonate, 0.025mol vanadium oxide, 0.075mol ammonium dihydrogen phosphate, 1.5g lignocellulosic are added in ball grinder, add 40ml acetone, with wet ball grinding mixing 24h, obtain mixing material.Mixing material after dry 2h under 120 ℃, is carried out pre-burning with 350 ℃ of insulation 10h under the protection of nitrogen, obtain the vanadium phosphate cathode material presoma.
Described vanadium phosphate cathode material presoma is carried out sintering with 660 ℃ of insulation 5h under the protection of nitrogen, the product after sintering is vanadium phosphate cathode material.Above-mentioned vanadium phosphate cathode material, 1.71g acetylene black, 1.71g Kynoar and the 20g1-N-methyl-2-2-pyrrolidone N-of 18g after fully grinding is modulated into slurry, described slurry is coated on aluminium foil, dry 2h, obtain lithium ion cell positive under 120 ℃.
The lithium ion cell positive that obtains with Comparative Examples 2 with the negative pole of lithium sheet as battery, prepares half-cell as the positive pole of battery.
Under 25 ℃ of conditions, measure the normalization discharge capacity of the half-cell that obtains when 0.1C, 0.25C, 0.5C, 1C and 1.5C multiplying power, the results are shown in Figure 9, Fig. 9 is the electrode high rate performance figure of the half-cell of Comparative Examples 2 preparations of the present invention.Take the high discharge capacity of 0.1C as 1, in Fig. 9,1 is the normalization discharge capacity of half-cell when 0.1C of Comparative Examples 2 preparations, 2 is the normalization discharge capacity of half-cell when 0.25C of Comparative Examples 2 preparations, 3 is the normalization discharge capacity of half-cell when 0.5C of Comparative Examples 2 preparations, 4 is the normalization discharge capacity of half-cell when 1C of Comparative Examples 2 preparations, and 5 is the normalization discharge capacity of half-cell when 1.5C of Comparative Examples 2 preparations.
By Fig. 8 and Fig. 9 as can be known, compare with the half-cell of Comparative Examples 2 preparations, the discharge-rate performance is good first for the prepared half-cell of the embodiment of the present invention 10, and discharge first normalization capacity and discharge platform are all high.
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a lithium ion cell positive comprises the following steps:
A) with precursor of lithium ionic cell positive material, binding agent and dispersant, make slurry;
Described precursor of lithium ionic cell positive material is ferric lithium phosphate precursor or phosphoric acid vanadium lithium presoma;
B) described slurry is coated on the non-woven fabric type film, obtains the lithium ion cell positive presoma after drying;
C) under the condition of protective gas, described lithium ion cell positive presoma is carried out sintering, obtain lithium ion cell positive.
2. preparation method according to claim 1, is characterized in that, described non-woven fabric type film is one or more in polypropylene fibre, terylene, polyamide fibre, viscose rayon, acrylic fibers, polyethylene and paper.
3. preparation method according to claim 1, is characterized in that, described binding agent is one or more in Kynoar, polytetrafluoroethylene, sodium carboxymethylcellulose and butadiene-styrene rubber.
4. preparation method according to claim 1, is characterized in that, described dispersant be in 1-Methyl-2-Pyrrolidone, ethanol, distilled water, deionized water and acetone one or more.
5. preparation method according to claim 1, is characterized in that, described protective gas is one or more in argon gas, nitrogen and helium.
6. preparation method according to claim 1, is characterized in that, the temperature of described sintering is 550 ~ 900 ℃, and the time of sintering is 2 ~ 20h.
7. preparation method according to claim 1, is characterized in that, the mass ratio of described precursor of lithium ionic cell positive material, binding agent and dispersant is (5 ~ 10): (1 ~ 5): (10 ~ 15).
8. preparation method according to claim 1, is characterized in that,
Described ferric lithium phosphate precursor is prepared as follows: after lithium source, source of iron, phosphorus source, carbon source and solvent, ball milling, drying, calcining, obtain ferric lithium phosphate precursor;
Described phosphoric acid vanadium lithium presoma is prepared as follows: after lithium source, vanadium source, phosphorus source, carbon source and solvent, ball milling, drying, calcining, obtain the phosphoric acid vanadium lithium presoma.
9. preparation method according to claim 8, is characterized in that,
Described lithium source be in lithium carbonate, lithium dihydrogen phosphate, lithium acetate, lithium nitrate and lithium hydroxide one or more;
Described source of iron be in ferrous oxalate, ferrous acetate, ferric oxalate, ferric acetate, ferric nitrate, ferric phosphate, di-iron trioxide, tri-iron tetroxide and ferrous oxide one or more;
Described vanadium source be in vanadic oxide, vanadium trioxide, vanadium dioxide and ammonium metavanadate one or more;
Described phosphorus source is one or more in ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ferric phosphate;
Described carbon source is lignocellulosic;
Described solvent be in deionized water, distilled water, industrial alcohol, absolute ethyl alcohol and acetone one or more.
10. lithium ion cell positive by the described preparation method of claim 1 ~ 9 any one preparation.
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| CN115819072A (en) * | 2022-12-15 | 2023-03-21 | 楚能新能源股份有限公司 | Ternary cathode material and preparation method and application thereof |
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| CN103326020A (en) * | 2013-06-05 | 2013-09-25 | 湖南工业大学 | Process for preparing lithium iron phosphate composite cathode material |
| CN103326020B (en) * | 2013-06-05 | 2016-05-04 | 湖南工业大学 | A kind of preparation method of iron phosphate compound anode material of lithium |
| CN105810906A (en) * | 2016-03-17 | 2016-07-27 | 齐鲁工业大学 | Preparation method of composite positive electrode material Li2NaV2(PO4)3/Li3V2(PO4)3/C for lithium-ion battery |
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| CN105845909A (en) * | 2016-04-27 | 2016-08-10 | 深圳市德方纳米科技股份有限公司 | Positive electrode active material for lithium ion battery, preparation method for positive electrode active material, and lithium ion battery |
| CN105845909B (en) * | 2016-04-27 | 2021-10-12 | 深圳市德方纳米科技股份有限公司 | Lithium ion battery positive electrode active material, preparation method thereof and lithium ion battery |
| CN109065840A (en) * | 2018-07-13 | 2018-12-21 | 惠州市智键科技有限公司 | A kind of based lithium-ion battery positive plate and preparation method thereof |
| CN114613945A (en) * | 2022-04-02 | 2022-06-10 | 北京师范大学 | Preparation method of lithium ion battery anode |
| CN115819072A (en) * | 2022-12-15 | 2023-03-21 | 楚能新能源股份有限公司 | Ternary cathode material and preparation method and application thereof |
| CN115819072B (en) * | 2022-12-15 | 2023-07-21 | 楚能新能源股份有限公司 | Ternary positive electrode material, and preparation method and application thereof |
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