CN106025215A - Preparation method for graphene-based composite nickel-cobalt-magnesium-titanium quaternary positive electrode material - Google Patents
Preparation method for graphene-based composite nickel-cobalt-magnesium-titanium quaternary positive electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method for a graphene-based composite nickel-cobalt-magnesium-titanium quaternary positive electrode material. The nickel-cobalt-magnesium-titanium quaternary positive electrode material is prepared by a chemical coprecipitation method; then the nickel-cobalt-magnesium-titanium quaternary positive electrode material is mixed with a solid carbon source, and then is subjected to ball milling to obtain a mixture; the obtained mixture is evaporated to the surface of a silicon substrate through an organic evaporation film coater to obtain a sample A; the sample A is put into a metal electron beam evaporation film coater; a metal catalyst is uniformly evaporated on the surface of the sample A to obtain a sample B; and the sample B is put into a quartz tube and then put into a tubular furnace to be subjected to vacuum sintering to obtain the graphene-based composite nickel-cobalt-magnesium-titanium quaternary positive electrode material. The conductivity and the safety performance of the positive electrode material can be greatly improved; the specific energy and specific power of the lithium ion battery can be remarkably increased; and in addition, due to the two-dimensional nano layered structure and the relatively large specific surface area of the graphene, the conductivity and the stability of the composite modified material can be improved consequently.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, be specifically related to the preparation method of a kind of graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode.
Background technology
Along with the needs of national economy transition, in 12 planning periods to the development of New Energy Industry and attention, the energy density of the bottleneck problem battery of restriction new-energy automobile in the urgent need to address and safety issue.We mainly have cobalt acid lithium, lithium nickelate, LiMn2O4, ternary material and LiFePO4 etc. by known ion battery positive electrode, but owing to cobalt resource is deficient, and toxicity is relatively big, causes cobalt acid lithium production cost to remain high, and environment is created irreversible impact;Lithium nickelate rich material resources all has advantage in the performance of gram volume in terms of specific energy, but its cycle performance is poor, limits the application of its industrialization;LiMn2O4 has the advantage such as aboundresources, low cost, pollution-free, safety good, good rate capability, but its cycle performance and electrochemical stability are poor, and greatly limit its industrialization;The safety of LiFePO 4 material and cycle life have significant advantage, but material self compacted density is the lowest, causes battery specific energy the highest, so limiting the space that car load promotes in terms of course continuation mileage.Owing to the specific capacity of positive electrode is relatively low, and need again the irreversible capacity loss of added burden negative pole, therefore improve the energy density of positive electrode and safety and be always the key point of Study on Li-ion batteries.Stratiform nickel cobalt magnesium titanium quaternary material has the advantage such as high-energy-density, relatively low, the stable cycle performance of cost, can effectively make up cobalt acid lithium, lithium nickelate, the respective deficiency of LiMn2O4, therefore the study hotspot being developed into positive electrode field of quaternary material.
Graphene is as the novel lamellar material with carbon element of a kind of two dimension hexagonal lattice structure, and it is to be made up of the carbon atom of sp2 hydridization, and its structure is close-packed arrays and presents bi-dimensional cellular shape grid, has the highest electric conductivity and the biggest specific surface area simultaneously;Graphene has good electric conductivity and stability determines it and can prepare nano composite material as conducting base, can improve the electric conductivity of composite;The two-dimensional nano layer structure of Graphene and bigger specific surface area, make again it can increase the electric conductivity of composite modification material and stability.Therefore, quaternary nickel cobalt magnesium titanium positive electrode is combined with Graphene, prepare a kind of novel graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode, electric conductivity and the security performance of positive electrode can be substantially improved, significantly improve specific energy and the specific power of lithium ion battery.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of electric conductivity and the most improved graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode of specific energy, this graphene-based compound quaternary positive electrode has high electric conductivity and stability, thus overcomes positive electrode electric conductivity in prior art the highest and the problem such as specific energy is low.
The preparation method of a kind of graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode, comprises the steps:
(1) nickel cobalt magnesium titanium quaternary positive electrode Li (Ni is prepared by chemical coprecipitationxCoyMgzTiz)O2, wherein x+y+2z=1,0.7≤x < 1,0.05≤y≤0.1,0.05≤z≤0.1;
(2) carry out mixing for 3:0.1-1 in mass ratio by nickel cobalt magnesium titanium quaternary positive electrode and solid carbon source, ball milling, obtain mixture;
(3) mixture is evaporated to silicon substrate surface by evaporated organic film instrument, is obtained sample A;
(4) sample A is put in metal electron beam evaporation plated film instrument, metallic catalyst is deposited with equably on the surface of sample A, i.e. can get sample B;
(5) it is placed in again after sample B being placed in quartz ampoule in tube furnace and carries out vacuum-sintering, i.e. obtain graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode.
Scheme further, the preparation method of the nickel cobalt magnesium titanium quaternary positive electrode in described step (1) is as follows: by the mol ratio of metallic element, soluble nickel salt, soluble cobalt, solubility magnesium salt and solubility titanium salt are configured to the mixed aqueous solution of 0.1-1mol/L, then mixed aqueous solution is added together with complexing agent aqueous solution, precipitant aqueous solution stirring in reactor carry out coprecipitation reaction;Reaction precipitation thing through filtering, washing, be dried, obtain spherical precursor;Again for 1:0.5-0.6, presoma is carried out ball milling in molar ratio with lithium source to mix, and calcine under oxygen atmosphere, i.e. can get nickel cobalt magnesium titanium quaternary positive electrode Li (NixCoyMgzTiz)O2, wherein x+y+2z=1,0.7≤x < 1,0.05≤y≤0.1,0.05≤z≤0.1.
Further scheme, the concentration of described complexing agent aqueous solution is 0.01-1mol/L, and the concentration of precipitant aqueous solution is 0.5-1.5mol/L.
Further scheme, described soluble nickel salt is one or more in the halogenide of nickel sulfate, nickel nitrate, nickel;
Described soluble cobalt is one or more in the halogenide of cobaltous sulfate, cobalt nitrate, cobalt;
Described solubility magnesium salt is one or more in the halogenide of magnesium sulfate, magnesium nitrate, magnesium;
Described solubility titanium salt is one or more in the halogenide of titanyl sulfate, butyl titanate, titanium;
Described lithium source is one or more in lithium nitrate, lithium carbonate, Lithium hydrate;
Described chelating agent is one or more in sodium tartrate, sodium citrate, sodium pyrophosphate, sodium tripolyphosphate;
Described precipitant is one or more in sodium carbonate, manganese carbonate, sodium hydroxide.
Further scheme, in described reactor stirring carry out the temperature of coprecipitation reaction be about 30-50 DEG C, mixing speed be 600-1000 rev/min, the response time is 2-5h;In described reactor, the pH of reactant solution is 7-8;The temperature of described calcining is 600-1000 DEG C, the time is 16-24h.
Scheme further, the ball milling in described step (2) is the planetary ball mill ball milling 2-6h using rotating speed to be 300-500 rev/min;Described solid carbon source is at least one in glucose, methane, Benzo[b (Pentacene), 8-hydroxyquinoline magnesium (Alq3), 2,4,6-triphen basic ring boron nitrogen six alkane (TPB).
Scheme, is pure silicon chip at the bottom of the reactive group of the evaporated organic film instrument in described step (3) further, and the speed controlling evaporated organic film instrument is 0.5-1g/cm2·s。
Scheme further, the metallic catalyst in described step (4) is one or more in copper, platinum, silver, and its consumption is 0.1-5g.
Scheme further, the power of the metal electron beam evaporation plated film instrument in described step (4) is 6-8%;The evaporation rate of metallic catalyst is 1-2g/cm2·s。
Scheme further, in described step (5), vacuum-sintering refers to be evacuated to tube furnace below 5Pa, and is passed through H2With the gaseous mixture atmosphere of Ar, it is that 10 DEG C/min maintains 30-40min after room temperature is warming up to 950-1050 DEG C with heating rate.
So the application is relative to prior art, have the advantages that
1, the present invention select four kinds of metallic elements as positive electrode because Co, Ti, Mg these three element be mixed with the capacity beneficially improving and improving positive electrode, it is possible to decrease Co4+With the extent of reaction that LiPF6 in electrolyte produces HF.Simultaneously as there is the incorporation of alkaline-earth metal Mg, material internal can be caused to produce the quick transmission of defect, beneficially electric charge, thus improve fast charging and discharging ability and the cycle performance of quaternary nickel cobalt magnesium titanium (LNCMTO) positive electrode.
2, graphene-based compound nickel cobalt aluminum titanium quaternary positive electrode prepared by the present invention, can be substantially improved electric conductivity and the security performance of positive electrode, significantly improve specific energy and the specific power of lithium ion battery.This is owing to Graphene has good electric conductivity and stability, so it is prepared nano composite material as conducting base and nickel cobalt aluminum titanium quaternary material, can improve the electric conductivity of composite;Further, since the two-dimensional nano layer structure of Graphene and bigger specific surface area, therefore increase electric conductivity and the stability of composite modification material.
3, carbon source and nickel cobalt magnesium titanium quaternary material are carried out ball milling by the present invention is to make the two carry out to be sufficiently mixed uniformly, during sintering and reducing, catalyst can carbon source reduce after obtain the target product of perfect cladding.
4, the present invention uses evaporated organic film instrument to be evaporated making quaternary material the most successively be arranged in above silicon substrate with the molecule of the mixture of carbon source;Then metal electron beam evaporation plated film instrument is used to make the catalyst such as copper, platinum, silver evaporate on preamble sample with molecular forms equably.This kind can make catalyst molecule layer carbon source fully be reduced in the sintering stage in molecular stacks mode, obtains perfect graphene-based compound quaternary positive electrode.
Detailed description of the invention
For making those skilled in the art be more fully understood that technical scheme, below in conjunction with detailed description of the invention, the present invention is described in further detail.
Embodiment 1
Step one, prepared nickel cobalt magnesium titanium quaternary positive electrode by chemical coprecipitation
It is first according to predetermined product each component transition metal ratio and calculates and weigh nickel sulfate, cobaltous sulfate, magnesium sulfate and titanyl sulfate, above-mentioned material is formulated as the solution a that nickel cobalt magnesium titanium melting concn is 0.5mol/L again, sodium tartrate is formulated as the solution b of 0.05mol/L, sodium carbonate is formulated as the solution c of 1mol/L;Solution a, solution b and solution c, at about 40 DEG C, are added in reactor by control system reaction temperature, control mixing speed 800 revs/min, and regulation pH value of solution is 7.5, response time 3h.After reaction terminates, carrying out precipitate filtering, wash, be dried, baking temperature is 100 DEG C, the time is 24h, obtains the spherical precursor being dried.Again by presoma with lithium carbonate according to presoma: lithium carbonate=1:0.5 ratio mixes, under oxygen atmosphere calcine, temperature is 700 DEG C, and the time is 20h, i.e. can get nickel cobalt titanium magnesium quaternary positive electrode.
Step 2, by solid carbon source glucose and nickel cobalt magnesium titanium quaternary positive electrode (LNCMT material) prepared according to mass ratio be 3:1 carry out mixing, ball milling, the rotating speed controlling planetary ball mill is 500 revs/min, Ball-milling Time is 4h, i.e. can get sample A.
Step 3, by prepared sample A by evaporated organic film instrument be evaporated to cleaning silicon substrate surface, control molecule evaporation rate be 0.5g/cm2About s, obtaining thickness at silicon chip surface is the uniform little molecular layer of 5mm, is sample B.
Step 4, prepared sample B is put in metal electron beam evaporation plated film instrument, choose metallic copper as catalyst, control plant capacity 7%, thus control the evaporation rate of copper about at 1g/cm2S so that the thickness of copper is 200nm, and uniformly evaporation, at this sample surfaces, i.e. obtains sample C.
Step 5, prepared sample C is placed in quartz ampoule after be placed in again in tube furnace, its vacuum is evacuated to below 5Pa, and is passed through reducibility gas H2With protection gas Ar, control heating rate and be increased to 1000 DEG C at 10 DEG C/min, after maintaining 30min, naturally cool to room temperature, i.e. can obtain the graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode of cladding.
Embodiment 2
Step one, prepared nickel cobalt magnesium titanium quaternary positive electrode by chemical coprecipitation;
It is first according to predetermined product each component transition metal ratio and calculates and weigh nickel nitrate, cobalt nitrate, magnesium nitrate and butyl titanate, above-mentioned material is formulated as the solution a that nickel cobalt magnesium titanium melting concn is 0.1mol/L again, sodium citrate is formulated as the solution b of 1mol/L, sodium hydroxide is formulated as the solution c of 1.5mol/L;Solution a, solution b and solution c, at about 40 DEG C, are added in reactor by control system reaction temperature, control mixing speed 600 revs/min, and regulation pH value of solution is 7, response time 2h.After reaction terminates, carrying out precipitate filtering, wash, be dried, baking temperature is 100 DEG C, the time is 24h, obtains the spherical precursor being dried.Again by presoma with lithium carbonate according to presoma: lithium carbonate=1:0.5 ratio mixes, under oxygen atmosphere calcine, temperature is 600 DEG C, and the time is 24h, i.e. can get nickel cobalt titanium magnesium quaternary positive electrode.
Step 2, by solid carbon source Benzo[b and nickel cobalt magnesium titanium quaternary positive electrode (LNCMT material) prepared in step one according to mass ratio be 3:0.1 carry out mixing, ball milling, the rotating speed controlling planetary ball mill is 300 revs/min, Ball-milling Time is 6h, i.e. obtains sample A.
Step 3, by prepared sample A by evaporated organic film instrument be evaporated to cleaning silicon substrate surface, control molecule evaporation rate be 1g/cm2About s, obtaining thickness at silicon chip surface is the uniform little molecular layer of 5mm, is sample B.
Step 4, prepared sample B is put in metal electron beam evaporation plated film instrument, choose argent as catalyst, control plant capacity 6%, thus control the evaporation rate of copper about at 1g/cm2S so that the thickness of copper is 200nm, and uniformly evaporation, at this sample surfaces, i.e. obtains sample C.
Step 5, prepared sample C is placed in quartz ampoule after be placed in again in tube furnace, vacuum is evacuated to below 5Pa, and is passed through reducibility gas H2With protection gas Ar, control heating rate and be increased to 950 DEG C at 10 DEG C/min, after maintaining 30min, naturally cool to room temperature, i.e. can obtain the graphene-based nickel cobalt magnesium titanium quaternary positive electrode of cladding.
Embodiment 3
Step one, prepared nickel cobalt magnesium titanium quaternary positive electrode by chemical coprecipitation;
It is first according to predetermined product each component transition metal ratio and calculates and weigh nickel sulfate, cobaltous sulfate, magnesium sulfate and titanyl sulfate, above-mentioned material is formulated as the solution a that nickel cobalt magnesium titanium melting concn is 1mol/L again, sodium pyrophosphate is formulated as the solution b of 0.1mol/L, sodium carbonate is formulated as the solution c of 0.5mol/L;Solution a, solution b and solution c, at about 40 DEG C, are added in reactor by control system reaction temperature, control mixing speed 1000 revs/min, and regulation pH value of solution is 8, response time 5h.After reaction terminates, carrying out precipitate filtering, wash, be dried, baking temperature is 100 DEG C, the time is 24h, obtains the spherical carbonate presoma being dried.Again by presoma with lithium carbonate according to presoma: lithium carbonate=1:0.6 ratio mixes, under oxygen atmosphere calcine, temperature is 1000 DEG C, and the time is 16h, i.e. can get nickel cobalt titanium magnesium quaternary positive electrode.
Step 2, by solid carbon source 8-hydroxyquinoline magnesium and nickel cobalt magnesium titanium quaternary positive electrode (LNCMT material) prepared in step one according to mass ratio be 3:0.5 carry out mixing, ball milling, the rotating speed controlling planetary ball mill is 500 revs/min, Ball-milling Time is 2h, i.e. obtains sample A.
Step 3, by prepared sample A by evaporated organic film instrument be evaporated to cleaning silicon substrate surface, control molecule evaporation rate be 0.8g/cm2About s, obtaining thickness at silicon chip surface is the uniform little molecular layer of 5mm, is sample B.
Step 4, prepared sample B is put in metal electron beam evaporation plated film instrument, choose metallic copper as catalyst, control plant capacity 8%, thus control the evaporation rate of copper about at 1g/cm2S so that the thickness of platinum is 200nm, and uniformly evaporation, at this sample surfaces, i.e. obtains sample C.
Step 5, being placed in quartz ampoule by prepared sample C and be placed in tube furnace, vacuum is evacuated to below 5Pa, and is passed through reducibility gas H2With protection gas Ar, control heating rate and be increased to 1050 DEG C at 10 DEG C/min, after maintaining 30min, naturally cool to room temperature, i.e. can obtain the graphene-based nickel cobalt magnesium titanium quaternary positive electrode of cladding.
Graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode embodiment 1-3 prepared respectively and nickel cobalt magnesium titanium quaternary positive electrode, nickel-cobalt-manganese ternary material, respectively as the positive electrode of battery, are prepared as battery (remaining condition is identical in addition to positive electrode) with metal lithium sheet for negative material.Capability retention after the detection discharge capacity first of battery, internal resistance, room temperature circulate 300 times the most respectively, concrete data are as shown in table 1 below:
Table 1:
Can draw from upper table 1: the present invention uses compared with the lithium ion battery that graphene-based compound nickel cobalt magnesium titanium quaternary material uses nickel cobalt magnesium titanium quaternary positive electrode or nickel-cobalt-manganternary ternary anode material to prepare as cell positive material as the lithium ion battery that cell positive material prepares with routine, it has, and discharge capacity is high, the internal resistance of cell is little, room temperature capability retention height and cyclical stability advantages of higher.And the preparation method of the present invention is simple, low cost, can be used for large-scale production.
The above is only the detailed description of the invention of the application; it should be pointed out that, for those skilled in the art, on the premise of without departing from the application principle; can also make some improvements and modifications, these improvements and modifications also should be regarded as the protection domain of the application.
Claims (10)
1. the preparation method of a graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode, it is characterised in that: comprise the steps:
(1) nickel cobalt magnesium titanium quaternary positive electrode Li (Ni is prepared by chemical coprecipitationxCoyMgzTiz)O2, wherein x+y+2z=1,0.7≤x < 1,0.05≤y≤0.1,
0.05≤z≤0.1;
(2) carry out mixing for 3:0.1-1 in mass ratio by nickel cobalt magnesium titanium quaternary positive electrode and solid carbon source, ball milling, obtain mixture;
(3) mixture is evaporated to silicon substrate surface by evaporated organic film instrument, is obtained sample A;
(4) sample A is put in metal electron beam evaporation plated film instrument, metallic catalyst is deposited with equably on the surface of sample A, i.e. can get sample B;
(5) it is placed in again after sample B being placed in quartz ampoule in tube furnace and carries out vacuum-sintering, i.e. obtain graphene-based compound nickel cobalt magnesium titanium quaternary positive electrode.
Preparation method the most according to claim 1, it is characterized in that: the preparation method of the nickel cobalt magnesium titanium quaternary positive electrode in described step (1) is as follows: by the mol ratio of metallic element, soluble nickel salt, soluble cobalt, solubility magnesium salt and solubility titanium salt are configured to the mixed aqueous solution of 0.1-1 mol/L, then mixed aqueous solution is added together with complexing agent aqueous solution, precipitant aqueous solution stirring in reactor carry out coprecipitation reaction;Reaction precipitation thing through filtering, washing, be dried, obtain spherical precursor;Again for 1:0.5-0.6, presoma is carried out ball milling in molar ratio with lithium source to mix, and calcine under oxygen atmosphere, i.e. can get nickel cobalt magnesium titanium quaternary positive electrode Li (NixCoyMgzTiz)O2, wherein x+y+2z=1,0.7≤x < 1,0.05≤y≤0.1,
0.05≤z≤0.1。
Preparation method the most according to claim 2, it is characterised in that: the concentration of described complexing agent aqueous solution is 0.01-1mol/L, and the concentration of precipitant aqueous solution is 0.5-1.5mol/L.
Preparation method the most according to claim 2, it is characterised in that: described soluble nickel salt is one or more in the halogenide of nickel sulfate, nickel nitrate, nickel;
Described soluble cobalt is one or more in the halogenide of cobaltous sulfate, cobalt nitrate, cobalt;
Described solubility magnesium salt is one or more in the halogenide of magnesium sulfate, magnesium nitrate, magnesium;
Described solubility titanium salt is one or more in the halogenide of titanyl sulfate, butyl titanate, titanium;
Described lithium source is one or more in lithium nitrate, lithium carbonate, Lithium hydrate;
Described chelating agent is one or more in sodium tartrate, sodium citrate, sodium pyrophosphate, sodium tripolyphosphate;
Described precipitant is one or more in sodium carbonate, manganese carbonate, sodium hydroxide.
Preparation method the most according to claim 2, it is characterised in that: in described reactor stirring carry out the temperature of coprecipitation reaction be about 30-50 DEG C, mixing speed be 600-1000 rev/min, the response time is 2-5h;In described reactor, the pH of reactant solution is 7-8;The temperature of described calcining is 600-1000 DEG C, the time is 16-24h.
Preparation method the most according to claim 1, it is characterised in that: the ball milling in described step (2) is the planetary ball mill ball milling 2-6h using rotating speed to be 300-500 rev/min;Described solid carbon source is at least one in glucose, methane, Benzo[b (Pentacene), 8-hydroxyquinoline magnesium (Alq3), 2,4,6-triphen basic ring boron nitrogen six alkane (TPB).
Preparation method the most according to claim 1, it is characterised in that: being pure silicon chip at the bottom of the reactive group of the evaporated organic film instrument in described step (3), the speed controlling evaporated organic film instrument is 0.5-1g/cm2·s。
Preparation method the most according to claim 1, it is characterised in that: the metallic catalyst in described step (4) is one or more in copper, platinum, silver, and its consumption is 0.1-5g.
Preparation method the most according to claim 1, it is characterised in that: the power of the metal electron beam evaporation plated film instrument in described step (4) is 6-8%;The evaporation rate of metallic catalyst is 1-2 g/cm2·s。
Preparation method the most according to claim 1, it is characterised in that: in described step (5), vacuum-sintering refers to be evacuated to tube furnace below 5Pa, and is passed through H2With the gaseous mixture atmosphere of Ar, it is that 10 DEG C/min maintains 30-40min after room temperature is warming up to 950-1050 DEG C with heating rate.
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