CN109616656A - The cladding LiNiPO positive electrode and preparation method that lithium battery is adulterated with copper magnesium - Google Patents

The cladding LiNiPO positive electrode and preparation method that lithium battery is adulterated with copper magnesium Download PDF

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CN109616656A
CN109616656A CN201811538700.0A CN201811538700A CN109616656A CN 109616656 A CN109616656 A CN 109616656A CN 201811538700 A CN201811538700 A CN 201811538700A CN 109616656 A CN109616656 A CN 109616656A
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linipo
lithium
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positive electrode
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蔡杰
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Yangzhou Hongtu Electronic Material Co.,Ltd.
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Chengdu Shui Long Tou Chemical Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The present invention relates to the technical fields of anode material of lithium battery, provide the cladding LiNiPO positive electrode and preparation method of a kind of lithium battery copper magnesium doping.This method in the presence of surfactants, the LiNiPO material LiNi of copper magnesium doping is made by hydro-thermal method1‑x‑yMgxCuyPO4, then by the covering liquid presoma sprayed deposit containing carboxymethyl cellulose, lithium carbonate and vanadic anhydride in LiNi1‑x‑yMgxCuyPO4Li is made through 550 ~ 650 DEG C of pre-burnings, 700 ~ 750 DEG C of sintering in particle surface3VO4The copper magnesium doping phosphoric acid nickel lithium anode material of/C mixing cladding.It is compared with the traditional method, LiNiPO positive electrode prepared by the present invention, chemical property is good, and ionic conductivity is high, and higher specific capacity, and good cycle are able to maintain under high magnification.

Description

The cladding LiNiPO positive electrode and preparation method that lithium battery is adulterated with copper magnesium
Technical field
The invention belongs to the technical fields of anode material of lithium battery, provide a kind of cladding phosphorus of lithium battery copper magnesium doping Sour nickel lithium anode material and preparation method.
Background technique
A kind of mechanism of new electrochemical power sources that lithium battery grows up as nineteen nineties, high with operating voltage, It is light-weight, specific capacity is high, self discharge is small, have extended cycle life, memory-less effect, it is safe and reliable, environmentally protective outstanding advantages of, at For the key areas for supporting electronic industry technology, it has also become the electronics such as mobile phone, laptop, digital camera, digital code camera The preferred power supply of the light-duty high power batteries such as the ideal energy of device miniaturization, and the following power vehicle, electric tool.
Lithium battery is usually made of anode, cathode and electrolyte three parts, and battery chemistries system determines the electricity of battery Chemical reaction, to determine the theoretical voltage of battery, theoretical specific capacity and theoretical specific energy.Wherein, positive electrode occupy compared with Large scale, the performance of positive electrode directly affect the performance of lithium ion battery, and cost also directly determines battery cost height, Research for positive electrode is to improve an importance of battery performance.
In anode material of lithium battery, the LiMPO with olivine-type structure4(M=Fe, Mn, Co, Ni) in recent years by A large amount of concerns, have that higher theoretical specific capacity, cycle performance be preferable, stable, safe, environmental-friendly, lower-price characteristic.Its In, nickel has the higher advantage of energy density, therefore, more and more for the research of LiNiPO positive electrode.
Chinese invention patent application number 201310279311.1 discloses a kind of Cathode material for lithium ion batteries phosphoric acid The in-situ carbon coating preparation method of nickel lithium.(1) Li source compound, nickelous source compound, phosphate and carbon source are dissolved in benzene In methanol aqueous solution；(2) in 100 ~ 200 DEG C of progress 4 ~ 10h hydro-thermal reactions；(3) it filters, it is clear with distilled water and dehydrated alcohol It washes；(4) 50 ~ 100 DEG C of dryings；(5) powder after drying is fully ground, is first pre-processed, then calcined and be made under high temperature Final product.The electric conductivity of LiNiPO positive electrode made from the invention is still not ideal enough, and high-multiplying power discharge specific capacity has Wait improve.
Chinese invention patent application number 201310402157.2 discloses a kind of solid-state reaction under microwave lithium ion battery phosphorus The method of sour nickel lithium/carbon composite material has many advantages, such as that potential high-energy-density, synthesis cost are low, environmentally friendly.The invention Choosing synthesis material includes lithium salts (or lithium hydroxide), phosphate, ammonium phosphate salt, nickel salt, conductive carbon black (or acetylene black or grape Sugar).After first by raw material using ball milling or stir process, when microwave power is 300 ~ 2000W, 5 ~ 30min of generated time can One-step synthesis lithium ion battery nickel phosphate lithium/carbon composite material.But it when composite material made from the invention is used for lithium battery, deposits The undesirable defect of charging and discharging capacity and cycle performance under high magnification.
In conclusion LiNiPO positive electrode there are ionic conductivities specific capacity poor, under high magnification and cycle performance Decline serious disadvantage, therefore develops the good LiNiPO anode material of cyclical stability under a kind of high conductivity and high magnification Material, has great significance.
Summary of the invention
As it can be seen that LiNiPO positive electrode there are ionic conductivities specific capacity poor, under high magnification and cycle performance decline Serious disadvantage.In response to this, the present invention proposes a kind of cladding LiNiPO positive electrode of lithium battery copper magnesium doping And preparation method, the LiNiPO positive electrode of preparation, chemical property is good, and ionic conductivity is high, is able to maintain under high magnification Higher specific capacity, and good cycle.
To achieve the above object, specific technical solution of the present invention is as follows:
The preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium, specific step is as follows for preparation:
(1) cetrimonium bromide, ethyl alcohol, deionized water are configured to mixed solution, lithium hydroxide is added and stirred Then dissolution is added ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate, stirs evenly, be transferred in hydrothermal reaction kettle, close It is heated to 120 ~ 125 DEG C of 4 ~ 5h of reaction under envelope state, then passes to nitrogen, is warming up to 170 ~ 180 DEG C the reaction was continued 1 ~ 2h, then Cooling, discharging filters, washing, vacuum drying, and the LiNiPO material of copper magnesium doping is made；
(2) carboxymethyl cellulose is added in deionized water, then lithium carbonate and five oxidations are added to being completely dissolved in heating stirring Two vanadium are dispersed, and are transferred in ball grinder, 8 ~ 10h of wet ball grinding, and covering liquid presoma is made in discharging；
(3) covering liquid presoma made from step (2) is deposited on to the phosphorus of the doping of copper magnesium made from step (1) as being spray-dried Sour nickel lithium material surface, is subsequently placed in Muffle furnace, 7 ~ 8h of pre-burning at 550 ~ 650 DEG C, then be warming up to 700 ~ 750 DEG C sintering 2 ~ 3h, carboxymethyl cellulose carbonization, lithium carbonate and vanadic anhydride generate Li3VO4, Li is made3VO4The copper of/C mixing cladding Magnesium doping phosphoric acid nickel lithium anode material.
Preferably, in step (1) described mixed solution, cetrimonium bromide, ethyl alcohol, deionized water mole Than for 1 ~ 3:30 ~ 70:30 ~ 70.
Since the chemical property of positive electrode and the grain diameter of LiNiPO are related, grain diameter is smaller, partial size divides Cloth is more uniform, and corresponding specific surface area is bigger, and the path that lithium ion is diffused into particle surface is shorter, and ion diffusion rates obtain It improves, so as to improve the chemical property of positive electrode, therefore, the present invention is using cetrimonium bromide as surface Activating agent, can play the purpose of control LiNiPO grain growth, the partial size of LiNiPO particle obtained 0.5 ~ 1 μm it Between.
The chemical formula of the doping phosphoric acid nickel lithium of synthesis is LiNi1-x-yMgxCuyPO4, therefore required raw material lithium hydroxide, phosphoric acid Ammonium dihydrogen, nickel sulfate, magnesium sulfate, copper sulphate molar ratio be 1:1:(1-x-y): x:y, still, since Li is in high-temperature process Volatile, when selecting raw material proportioning, lithium hydroxide answers excessive 10 ~ 20%, therefore, as a preferred solution of the present invention, step (1) The lithium hydroxide, ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate molar ratio be 1.1 ~ 1.2:1:(1-x-y): x:y, Wherein, x can be the value of one in 0.05,0.1,0.15,0.2, and y can be the value of one in 0.05,0.1,0.15,0.2.
Using metal ion mixing, the chemical property of LiNiPO not only can be improved, LiNiPO can also be improved High magnification stability and cycle performance.The magnesium ion and copper ion of incorporation replace part nickel ion, but not change nickel phosphate The crystal structure of lithium, but reach the electrochemical kinetics energy of enhancing LiNiPO by reinforcing the contraction inside crystal lattices Power improves reversible capacity, to realize good cycle performance.Due to the increase of the molar ratio with Doped ions, phosphoric acid The particle size presentation of nickel lithium first reduces the trend increased afterwards, and the particle to guarantee obtained copper magnesium doping phosphoric acid nickel lithium is small and equal It is even, it is preferred that value of the value of x no more than 0.2, y is not more than 0.2.
Preferably, step (1) the vacuum drying temperature is 40 ~ 60 DEG C, and the time is 8 ~ 10h.
Preferably, in the preparation of step (2) the covering liquid presoma, carboxymethyl cellulose, deionized water, lithium carbonate, The molar ratio of vanadic anhydride is 3 ~ 5:10 ~ 20:3:1.
Preferably, step (2) heating temperature is 50 ~ 70 DEG C.
The present invention is using carboxymethyl cellulose as carbon source, the LiNiPO particle surface shape adulterated by high temperature sintering in copper magnesium At carbon-coating, promote the formation of conductive network, further, using lithium carbonate and vanadic anhydride as raw material in-situ preparation Li3VO4With Carbon-coating forms mixing cladding, one side Li3VO4Incomplete carbon coating layer can be repaired, on the other hand due to Li3VO4With the hole 3D Road structure can provide more multichannel for the diffusion of lithium ion, significantly improve the diffusion rate of lithium ion, and improve doping The high rate capability of LiNiPO.Pass through Li3VO4The mixing of/C coats, and can also prevent dissolution of the electrolyte to positive electrode.
Preferably, the spraying revolving speed of step (3) described spray drying is 15000 ~ 18000r/min, and spraying disk diameter is 120~150mm。
Preferably, the weight ratio of step (3) the covering liquid presoma and copper magnesium doping phosphoric acid nickel lithium material is 1 ~ 2:10.
The present invention also provides a kind of cladding nickel phosphates that the lithium battery that above-mentioned preparation method is prepared is adulterated with copper magnesium Lithium anode material.The LiNiPO positive electrode is by Li3VO4/ C mixing cladding, and by copper, magnesium metal ion mixing, it is In the presence of surfactants, the LiNiPO material LiNi of copper magnesium doping is made by hydro-thermal method1-x-yMgxCuyPO4, then will Covering liquid presoma sprayed deposit containing carboxymethyl cellulose, lithium carbonate and vanadic anhydride is in LiNi1-x-yMgxCuyPO4? Grain surface is made through 550 ~ 650 DEG C of pre-burnings, 700 ~ 750 DEG C of sintering.The ionic conductivity of positive electrode obtained be 2.2 ~ 2.5×10-2S/cm, the first charge-discharge specific capacity of the manufactured button cell of assembling are 150 ~ 160mAh/g in 0.1C multiplying power, are filled 50 Zhou Houwei capacity retention ratio of discharge cycles is 94 ~ 96%；It is 135 ~ 145mAh/g, 50 Zhou Houwei of charge and discharge cycles under 1C multiplying power Capacity retention ratio is 90 ~ 93%；Under 5C multiplying power be 115 ~ 125mAh/g, 50 Zhou Houwei capacity retention ratio of charge and discharge cycles be 84 ~ 87%；It is 90 ~ 100mAh/g under 10C multiplying power, 50 Zhou Houwei capacity retention ratio of charge and discharge cycles is 75 ~ 78%.
The cladding LiNiPO positive electrode and preparation method that the present invention provides a kind of lithium batteries to be adulterated with copper magnesium, and it is existing There is technology to compare, the feature and excellent effect protruded is:
1. preparation method of the invention, by the control to grain growth, the grain diameter of LiNiPO positive electrode obtained Tiny and particle diameter distribution is uniform, and lithium ion diffusion path is short, and diffusion rate is high, and the chemical property of LiNiPO improves, ion Conductivity improves.
2. preparation method of the invention is doped LiNiPO by magnesium ion and copper ion, LiNiPO is improved Chemical property, specific capacity and cycle performance under high magnification.
3. preparation method of the invention, passes through Li3VO4/ C coats the mixing of doping phosphoric acid nickel lithium, can form complete carbon Clad conductive network, and more multichannel is provided for the diffusion of lithium ion, the diffusion rate of lithium ion is not only improved, but also improve The high rate capability of doping phosphoric acid nickel lithium can also prevent dissolution of the electrolyte to positive electrode.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) cetrimonium bromide, ethyl alcohol, deionized water are configured to mixed solution, lithium hydroxide is added and stirred Then dissolution is added ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate, stirs evenly, be transferred in hydrothermal reaction kettle, close It is heated to 123 DEG C of reaction 4.5h under envelope state, then passes to nitrogen, is warming up to 176 DEG C the reaction was continued 1.5h, it is then cooling, go out Material filters, washing, vacuum drying, and the LiNiPO material of copper magnesium doping is made；In mixed solution, cetyltrimethylammonium Base ammonium, ethyl alcohol, deionized water molar ratio be 2:50:55；Lithium hydroxide, ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate Molar ratio be 1.14:1:0.8:0.1:0.1；Vacuum drying temperature is 48 DEG C, time 9h；
(2) carboxymethyl cellulose is added in deionized water, then lithium carbonate and five oxidations are added to being completely dissolved in heating stirring Two vanadium are dispersed, and are transferred in ball grinder, wet ball grinding 9h, and covering liquid presoma is made in discharging；The system of covering liquid presoma In standby, carboxymethyl cellulose, deionized water, lithium carbonate, vanadic anhydride molar ratio be 4:16:3:1；Heating temperature is 58 ℃；
(3) covering liquid presoma made from step (2) is deposited on to the phosphorus of the doping of copper magnesium made from step (1) as being spray-dried Sour nickel lithium material surface, is subsequently placed in Muffle furnace, the pre-burning 7.5h at 590 DEG C, then is warming up to 730 DEG C of sintering 2.5h, is made Li3VO4The copper magnesium doping phosphoric acid nickel lithium anode material of/C mixing cladding；The spraying revolving speed of spray drying is 17000r/min, spraying Disk diameter is 130mm；The weight ratio of covering liquid presoma and copper magnesium doping phosphoric acid nickel lithium material is 1.4:10.
Embodiment 2
(1) cetrimonium bromide, ethyl alcohol, deionized water are configured to mixed solution, lithium hydroxide is added and stirred Then dissolution is added ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate, stirs evenly, be transferred in hydrothermal reaction kettle, close It is heated to 121 DEG C of reaction 5h under envelope state, then passes to nitrogen, is warming up to 172 DEG C the reaction was continued 2h, it is then cooling, discharge, take out Filter, washing, vacuum drying, are made the LiNiPO material of copper magnesium doping；In mixed solution, cetrimonium bromide, Ethyl alcohol, deionized water molar ratio be 1:40:45；Lithium hydroxide, ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate mole Than for 1.1:1:0.85:0.05:0.1；Vacuum drying temperature is 45 DEG C, time 9.5h；
(2) carboxymethyl cellulose is added in deionized water, then lithium carbonate and five oxidations are added to being completely dissolved in heating stirring Two vanadium are dispersed, and are transferred in ball grinder, wet ball grinding 8.5h, and covering liquid presoma is made in discharging；Covering liquid presoma In preparation, carboxymethyl cellulose, deionized water, lithium carbonate, vanadic anhydride molar ratio be 3:13:3:1；Heating temperature is 55 ℃；
(3) covering liquid presoma made from step (2) is deposited on to the phosphorus of the doping of copper magnesium made from step (1) as being spray-dried Sour nickel lithium material surface, is subsequently placed in Muffle furnace, the pre-burning 8h at 560 DEG C, then is warming up to 710 DEG C of sintering 3h, is made Li3VO4The copper magnesium doping phosphoric acid nickel lithium anode material of/C mixing cladding；The spraying revolving speed of spray drying is 16000r/min, spraying Disk diameter is 130mm；The weight ratio of covering liquid presoma and copper magnesium doping phosphoric acid nickel lithium material is 1.3:10.
Embodiment 3
(1) cetrimonium bromide, ethyl alcohol, deionized water are configured to mixed solution, lithium hydroxide is added and stirred Then dissolution is added ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate, stirs evenly, be transferred in hydrothermal reaction kettle, close It is heated to 14 DEG C of reaction 4h under envelope state, then passes to nitrogen, is warming up to 178 DEG C the reaction was continued 1h, it is then cooling, discharge, take out Filter, washing, vacuum drying, are made the LiNiPO material of copper magnesium doping；In mixed solution, cetrimonium bromide, Ethyl alcohol, deionized water molar ratio be 3:60:65；Lithium hydroxide, ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate mole Than for 1.2:1:0.65:0.2:0.15；Vacuum drying temperature is 55 DEG C, time 8.5h；
(2) carboxymethyl cellulose is added in deionized water, then lithium carbonate and five oxidations are added to being completely dissolved in heating stirring Two vanadium are dispersed, and are transferred in ball grinder, wet ball grinding 9.5h, and covering liquid presoma is made in discharging；Covering liquid presoma In preparation, carboxymethyl cellulose, deionized water, lithium carbonate, vanadic anhydride molar ratio be 4.5:18:3:1；Heating temperature is 65℃；
(3) covering liquid presoma made from step (2) is deposited on to the phosphorus of the doping of copper magnesium made from step (1) as being spray-dried Sour nickel lithium material surface, is subsequently placed in Muffle furnace, the pre-burning 7h at 620 DEG C, then is warming up to 740 DEG C of sintering 2h, is made Li3VO4The copper magnesium doping phosphoric acid nickel lithium anode material of/C mixing cladding；The spraying revolving speed of spray drying is 17000r/min, spraying Disk diameter is 140mm；The weight ratio of covering liquid presoma and copper magnesium doping phosphoric acid nickel lithium material is 1.7:10.
Embodiment 4
(1) cetrimonium bromide, ethyl alcohol, deionized water are configured to mixed solution, lithium hydroxide is added and stirred Then dissolution is added ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate, stirs evenly, be transferred in hydrothermal reaction kettle, close It is heated to 120 DEG C of reaction 5h under envelope state, then passes to nitrogen, is warming up to 170 DEG C the reaction was continued 2h, it is then cooling, discharge, take out Filter, washing, vacuum drying, are made the LiNiPO material of copper magnesium doping；In mixed solution, cetrimonium bromide, Ethyl alcohol, deionized water molar ratio be 1:30:30；Lithium hydroxide, ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate mole Than for 1.1:1:0.9:0.05:0.05；Vacuum drying temperature is 40 DEG C, time 10h；
(2) carboxymethyl cellulose is added in deionized water, then lithium carbonate and five oxidations are added to being completely dissolved in heating stirring Two vanadium are dispersed, and are transferred in ball grinder, wet ball grinding 8h, and covering liquid presoma is made in discharging；The system of covering liquid presoma In standby, carboxymethyl cellulose, deionized water, lithium carbonate, vanadic anhydride molar ratio be 3:10:3:1；Heating temperature is 50 ℃；
(3) covering liquid presoma made from step (2) is deposited on to the phosphorus of the doping of copper magnesium made from step (1) as being spray-dried Sour nickel lithium material surface, is subsequently placed in Muffle furnace, the pre-burning 8h at 550 DEG C, then is warming up to 700 DEG C of sintering 3h, is made Li3VO4The copper magnesium doping phosphoric acid nickel lithium anode material of/C mixing cladding；The spraying revolving speed of spray drying is 15000r/min, spraying Disk diameter is 120mm；The weight ratio of covering liquid presoma and copper magnesium doping phosphoric acid nickel lithium material is 1:10.
Embodiment 5
(1) cetrimonium bromide, ethyl alcohol, deionized water are configured to mixed solution, lithium hydroxide is added and stirred Then dissolution is added ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate, stirs evenly, be transferred in hydrothermal reaction kettle, close It is heated to 125 DEG C of reaction 4h under envelope state, then passes to nitrogen, is warming up to 180 DEG C the reaction was continued 1h, it is then cooling, discharge, take out Filter, washing, vacuum drying, are made the LiNiPO material of copper magnesium doping；In mixed solution, cetrimonium bromide, Ethyl alcohol, deionized water molar ratio be 3:70:70；Lithium hydroxide, ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate rub You are than being 1.2:1:0.6:0.2:0.2；Vacuum drying temperature is 60 DEG C, time 8h；
(2) carboxymethyl cellulose is added in deionized water, then lithium carbonate and five oxidations are added to being completely dissolved in heating stirring Two vanadium are dispersed, and are transferred in ball grinder, wet ball grinding 10h, and covering liquid presoma is made in discharging；Covering liquid presoma In preparation, carboxymethyl cellulose, deionized water, lithium carbonate, vanadic anhydride molar ratio be 5:20:3:1；Heating temperature is 70℃；
(3) covering liquid presoma made from step (2) is deposited on to the phosphorus of the doping of copper magnesium made from step (1) as being spray-dried Sour nickel lithium material surface, is subsequently placed in Muffle furnace, the pre-burning 7h at 650 DEG C, then is warming up to 750 DEG C of sintering 2h, is made Li3VO4The copper magnesium doping phosphoric acid nickel lithium anode material of/C mixing cladding；The spraying revolving speed of spray drying is 18000r/min, spraying Disk diameter is 150mm；The weight ratio of covering liquid presoma and copper magnesium doping phosphoric acid nickel lithium material is 2:10.
Embodiment 6
(1) cetrimonium bromide, ethyl alcohol, deionized water are configured to mixed solution, lithium hydroxide is added and stirred Then dissolution is added ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate, stirs evenly, be transferred in hydrothermal reaction kettle, close It is heated to 122 DEG C of reaction 4.5h under envelope state, then passes to nitrogen, is warming up to 175 DEG C the reaction was continued 1.5h, it is then cooling, go out Material filters, washing, vacuum drying, and the LiNiPO material of copper magnesium doping is made；In mixed solution, cetyltrimethylammonium Base ammonium, ethyl alcohol, deionized water molar ratio be 2:50:50；Lithium hydroxide, ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate Molar ratio be 1.15:1:0.7:0.15:0.15；Vacuum drying temperature is 50 DEG C, time 9h；
(2) carboxymethyl cellulose is added in deionized water, then lithium carbonate and five oxidations are added to being completely dissolved in heating stirring Two vanadium are dispersed, and are transferred in ball grinder, wet ball grinding 9h, and covering liquid presoma is made in discharging；The system of covering liquid presoma In standby, carboxymethyl cellulose, deionized water, lithium carbonate, vanadic anhydride molar ratio be 4:15:3:1；Heating temperature is 60 ℃；
(3) covering liquid presoma made from step (2) is deposited on to the phosphorus of the doping of copper magnesium made from step (1) as being spray-dried Sour nickel lithium material surface, is subsequently placed in Muffle furnace, the pre-burning 7.5h at 600 DEG C, then is warming up to 720 DEG C of sintering 2.5h, is made Li3VO4The copper magnesium doping phosphoric acid nickel lithium anode material of/C mixing cladding；The spraying revolving speed of spray drying is 16500r/min, spraying Disk diameter is 135mm；The weight ratio of covering liquid presoma and copper magnesium doping phosphoric acid nickel lithium material is 1.5:10.
Comparative example 1
In preparation process, metal ion mixing is not carried out to LiNiPO, other preparation conditions and embodiment 6 are consistent.
Comparative example 2
In preparation process, carbon coating only has been carried out to LiNiPO, Li is not used3VO4Mixing cladding is carried out, other preparation conditions It is consistent with embodiment 6.
Performance test:
(1) ionic conductivity: positive plate sample is made in positive electrode produced by the present invention, using four probe method, using conductance Rate tester measures the ionic conductivity of sample, and retest calculates average value；
(2) charge and discharge cycles test specific capacity: positive plate is made in positive electrode produced by the present invention, it is poly- with Celgard2400 Propylene microcellular film is diaphragm, the LiPF of 1mol/L6Mixed organic solvents (EC:DMC=1:1, volume ratio) be electrolyte, with gold Belonging to lithium piece is the button cell of model CR2025 to be assembled into the glove box full of argon gas, using battery performance to pole piece Test macro carries out charge and discharge cycles test, and charge and discharge Athens range is 2 ~ 4V, and testing multiplying power respectively is respectively 0.1C, 1C, 5C With under 10C multiplying power for the first time, 50 weeks charging and discharging capacities of circulation.
The data obtained is as shown in table 1.
Table 1:

Claims (9)

1. the preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium, which is characterized in that the copper magnesium is mixed Specific step is as follows for miscellaneous cladding LiNiPO preparation:
(1) cetrimonium bromide, ethyl alcohol, deionized water are configured to mixed solution, lithium hydroxide is added and stirred Then dissolution is added ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate, stirs evenly, be transferred in hydrothermal reaction kettle, close It is heated to 120 ~ 125 DEG C of 4 ~ 5h of reaction under envelope state, then passes to nitrogen, is warming up to 170 ~ 180 DEG C the reaction was continued 1 ~ 2h, then Cooling, discharging filters, washing, vacuum drying, and the LiNiPO material of copper magnesium doping is made；
(2) carboxymethyl cellulose is added in deionized water, then lithium carbonate and five oxidations are added to being completely dissolved in heating stirring Two vanadium are dispersed, and are transferred in ball grinder, 8 ~ 10h of wet ball grinding, and covering liquid presoma is made in discharging；
(3) covering liquid presoma made from step (2) is deposited on to the phosphorus of the doping of copper magnesium made from step (1) as being spray-dried Sour nickel lithium material surface, is subsequently placed in Muffle furnace, 7 ~ 8h of pre-burning at 550 ~ 650 DEG C, then be warming up to 700 ~ 750 DEG C sintering 2 ~ 3h, carboxymethyl cellulose carbonization, lithium carbonate and vanadic anhydride generate Li3VO4, Li is made3VO4The copper of/C mixing cladding Magnesium doping phosphoric acid nickel lithium anode material.
2. the preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium according to claim 1, special Sign is: in step (1) described mixed solution, cetrimonium bromide, ethyl alcohol, deionized water molar ratio be 1 ~ 3: 30~70:30~70。
3. the preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium according to claim 1, special Sign is: step (1) lithium hydroxide, ammonium dihydrogen phosphate, nickel sulfate, magnesium sulfate, copper sulphate molar ratio be 1.1 ~ 1.2: 1:(1-x-y): x:y, wherein x can be able to be in 0.05,0.1,0.15,0.2 for the value of one in 0.05,0.1,0.15,0.2, y One value.
4. the preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium according to claim 1, special Sign is: step (1) the vacuum drying temperature is 40 ~ 60 DEG C, and the time is 8 ~ 10h.
5. the preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium according to claim 1, special Sign is: in the preparation of step (2) the covering liquid presoma, carboxymethyl cellulose, deionized water, lithium carbonate, five oxidations two The molar ratio of vanadium is 3 ~ 5:10 ~ 20:3:1.
6. the preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium according to claim 1, special Sign is: step (2) heating temperature is 50 ~ 70 DEG C.
7. the preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium according to claim 1, special Sign is: the spraying revolving speed of step (3) described spray drying is 15000 ~ 18000r/min, and spraying disk diameter is 120 ~ 150mm.
8. the preparation method for the cladding LiNiPO positive electrode that lithium battery is adulterated with copper magnesium according to claim 1, special Sign is: the weight ratio of step (3) the covering liquid presoma and copper magnesium doping phosphoric acid nickel lithium material is 1 ~ 2:10.
9. the cladding LiNiPO that the lithium battery that any one of claim 1 ~ 8 preparation method is prepared is adulterated with copper magnesium is just Pole material.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111900377A (en) * 2020-08-04 2020-11-06 中国科学院物理研究所 Magnesium compound material and preparation method and application thereof
WO2024000101A1 (en) * 2022-06-27 2024-01-04 宁德时代新能源科技股份有限公司 Secondary battery, battery module, battery pack, and electrical device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009061845A1 (en) * 2007-11-05 2009-05-14 Board Of Regents, The University Of Texas System Rapid microwave-solvothermal synthesis and surface modification of nanostructured phospho-olivine cathodes for lithium ion batteries
CN102088072A (en) * 2011-01-14 2011-06-08 上海电力学院 Novel battery system of LiNiPO4/Li4Ti5O12 and preparation method thereof
CN102473911A (en) * 2009-07-31 2012-05-23 丰田自动车株式会社 Positive electrode active material and method for producing same
CN102496714A (en) * 2011-12-27 2012-06-13 天津力神电池股份有限公司 Anode active substance, production method thereof, and lithium ion battery employing anode active substance
CN103456950A (en) * 2013-07-09 2013-12-18 新疆师范大学 Green synthesis method for lithium-nickel phosphate/carbon composite material for lithium-ion battery
CN107706402A (en) * 2017-11-16 2018-02-16 东北大学秦皇岛分校 A kind of lithium manganese phosphate/carbon composite anode material of metallic element codope and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009061845A1 (en) * 2007-11-05 2009-05-14 Board Of Regents, The University Of Texas System Rapid microwave-solvothermal synthesis and surface modification of nanostructured phospho-olivine cathodes for lithium ion batteries
CN102473911A (en) * 2009-07-31 2012-05-23 丰田自动车株式会社 Positive electrode active material and method for producing same
CN102088072A (en) * 2011-01-14 2011-06-08 上海电力学院 Novel battery system of LiNiPO4/Li4Ti5O12 and preparation method thereof
CN102496714A (en) * 2011-12-27 2012-06-13 天津力神电池股份有限公司 Anode active substance, production method thereof, and lithium ion battery employing anode active substance
CN103456950A (en) * 2013-07-09 2013-12-18 新疆师范大学 Green synthesis method for lithium-nickel phosphate/carbon composite material for lithium-ion battery
CN107706402A (en) * 2017-11-16 2018-02-16 东北大学秦皇岛分校 A kind of lithium manganese phosphate/carbon composite anode material of metallic element codope and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ANAND等: "Structural, dielectric and conductivity studies of LiNi0.75Mg0.25-xCuxPO4 synthesized by solid state reaction method", 《PROCESSING AND APPLICATION OF CERAMICS》 *
BAO ZHANG等: "Enhanced electrochemical performance of LiNi0.8Co0.1Mn0.1O2 with lithium-reactive Li3VO4 coating", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
YOURONG WANG等: "Enhanced electrochemical performance of unique morphological LiMnPO4/C cathode material prepared by solvothermal method", 《SOLID STATE COMMUNICATIONS》 *
ZHIJIAN ZHANG等: "Enhanced electrochemical performance of nano LiMnPO4 with multifunctional surface co-coating of Li2TiO3 and carbon", 《SOLID STATE IONICS》 *
黄艳: "锂离子电池正极材料Li[Ni1-x-yCoxMny]O2的制备与表面改性研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111900377A (en) * 2020-08-04 2020-11-06 中国科学院物理研究所 Magnesium compound material and preparation method and application thereof
WO2024000101A1 (en) * 2022-06-27 2024-01-04 宁德时代新能源科技股份有限公司 Secondary battery, battery module, battery pack, and electrical device

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