CN106340642A - Long-circulation and high-capacity lithium battery positive electrode material and preparing method - Google Patents
Long-circulation and high-capacity lithium battery positive electrode material and preparing method Download PDFInfo
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention belongs to the technical field of lithium battery materials, particularly relates to a long-circulation and high-capacity lithium battery positive electrode material and further discloses a preparing method of the long-circulation and high-capacity lithium battery positive electrode material. The long-circulation and high-capacity lithium battery positive electrode material is a ternary lithium-nickel-manganese-cobalt positive electrode material, and an existing coprecipitation method and an existing high-temperature solid-phase method are combined. The method comprises the steps that firstly, by using the performance of an added precipitator and a catalyst, a precursor material with a mesoporous structure and a large specific surface area is obtained; then, a positive electrode material stable in performance is obtained through an optimized high-temperature sintering technology; then, modification with a metal salt modifying agent is adopted for assistance, and the ternary positive electrode material large in specific capacity, excellent in circulation performance, uniform in material and good in stability is obtained.
Description
Technical field
The invention belongs to lithium battery material technical field is and in particular to a kind of long circulating high-capacity lithium battery positive electrode,
And its preparation method is disclosed further.
Background technology
Lithium ion battery, as a kind of emerging energy, has high-energy, long-life, memory-less effect and low stain etc. excellent
Point, since the advent of the world just receives vast research and concern, is widely used in mobile phone, computer, electric bicycle, electronic
The multiple fields such as automobile, national defence.
Positive electrode is most important ingredient in lithium battery, directly determines the quality of lithium battery performance.At present, lithium from
The positive electrode that sub- battery adopts focuses primarily upon ternary material, mainly has cobalt acid lithium, LiFePO4, LiMn2O4 and nickel cobalt mangaic acid
The tertiary cathode materials such as lithium.With the development applying electrokinetic cell in electric automobile, due to the energy of LiFePO4 and LiMn2O4
Metric density is low to be required it is impossible to meet it；And nickle cobalt lithium manganate to have that specific capacity is high, heat stability is good and cheap etc. excellent
Point, is most potential one kind in anode material for lithium-ion batteries, has preferably in dynamic field such as electric motor car, electric tools
Application prospect.
At present, the preparation of ternary material mainly has sol-gel process, hydrothermal synthesis method, coprecipitation, high temperature solid-state method etc.
Method.
The chemical process of sol-gel process is by stock dispersion in a solvent first, is then passed through hydrolysis and generates work
Property monomer, then activated monomer carried out polymerization make colloidal sol, and then generate the gel with certain space structure, then pass through
It is dried and heat treatment prepares nickel-cobalt lithium manganate cathode material.But it is long to there is synthesis cycle in the method, industrialized production
The defect such as difficulty is larger.
Hydrothermal Synthesiss technology refers to the method carrying out chemosynthesis in the supersaturated aqueous solution of High Temperature High Pressure, belongs to humidifying
One kind of method synthesis.The general degree of crystallinity of powder using hydro-thermal method synthesis is higher, and can be made by optimum synthesis condition
Do not contain any water of crystallization, and the size of powder, uniformity, shape, composition can obtain strict control.But pass through
The ternary material of hydro-thermal method preparation, then the lot stability with material poor it is difficult to industrialization production.
Chemical coprecipitation refers to by the material mixing of different chemical composition under solution state, and adds people in mixed liquor
Suitable precipitant prepares presoma precipitate, then precipitate is dried or is calcined, thus corresponding powder body is obtained
The method of granule.Chemical coprecipitation is generally divided into direct chemical coprecipitation and indirect chemical coprecipitation.Directly chemistry is common
The sedimentation method are to be co-precipitated the salt of li, ni, co, mn simultaneously, and filtration washing carries out high-temperature roasting again and required ternary is obtained after being dried
Material.Indirect chemical co-precipitation rule is first synthesis ni, co, mn ternary mixing co-precipitation, then after filter washing is dried, with
Lithium salts mixed sintering is obtained；Or generate ni, co, mn ternary mixing co-precipitation after without filter but will comprise lithium salts and
The solution evaporation of mixing co-precipitation or lyophilization, then carry out high-temperature roasting to dried object again.Chemical coprecipitation method is permissible
Material is made to reach molecule or the mixing of atom dimension stoichiometric proportion, the particle diameter that is easy to get is little, the presoma of mix homogeneously, at present industry
Upper large-scale production.But the content of impurity and proportioning are difficult to precise control in coprecipitation gained sediment, simultaneously altogether
Each stage that precipitation is grown up to the rinsing precipitating, drying, calcining from co-precipitation, crystal grain during preparing powder body all may lead
Cause the formation of particle growth and aggregate, preparation process is wayward.
High-temperature solid phase reaction method is solid material mixture directly to carry out high temperature sintering in solid form with needed for synthesizing
The method of material.Nickle cobalt lithium manganate high temperature process heat mainly adopts various nickeliferous, cobalt, manganese salts or oxide or hydroxide
Through high-temperature nuclei after directly mixing with lithium salts.It is short that high temperature solid phase synthesis have a technological process, and equipment is simple, be easy to give birth on a large scale
The advantages of product, from the point of view of complex process degree, Financial cost and industrialization prospect, be to be hopeful most to develop into industrialized conjunction
Become technique.But current high temperature solid-state method also exists, and batch mixing is uneven, cannot form homogeneous eutectic and each batch quality
Unstable the problems such as, it is difficult to ensure that ni, co, mn each element is evenly distributed in building-up process, and the material morphology synthesizing is not advised
Then, thus leading to material circulation performance and specific capacity poor.
It can be seen that, develop a kind of simple and effective anode material of lithium battery preparation method, with obtain can be mass-produced, material
Uniformly, the excellent ternary material of good stability, specific capacity height, cycle performance, has positive meaning for Lithium Battery Industry development
Justice.
Content of the invention
For this reason, the technical problem to be solved is to provide a kind of long circulating high-capacity lithium battery positive electrode,
And disclose its preparation method further, and then obtain the tertiary cathode material that specific capacity is high, cycle performance is excellent.
For solve above-mentioned technical problem, the preparation method of long circulating high-capacity lithium battery positive electrode of the present invention,
Comprise the steps:
(1) prepare presoma: take nickel salt, cobalt salt and manganese salt to make mixing salt solution, add catalyst and precipitant mixes,
And carry out precipitation；To be precipitated be not further added by, filter taking precipitate washed, remove filtrate and drying, obtain final product positive pole material
Material precursor；
(2) prepare positive electrode: add lithium salt in described positive electrode material precursor, after grinding uniformly, enter
Row high temperature sintering curing reaction, obtains positive electrode；
(3) positive electrode is modified: takes slaine modifying agent to be dissolved in volatile organic solvent, and adds described positive electrode
Mix, to described organic solvent evaporating completely, high-temperature heat treatment is to dry, pulverize sieve under inert gas atmosphere for high-temperature stirring
Point, obtain final product described long circulating high-capacity lithium battery positive electrode.
In described step (1), described catalyst be one of Graphene, CNT, carbon nanocoils or acetylene black or
Several mixture；The addition of described catalyst accounts for the 0.5-1wt% of described nickel salt, cobalt salt and manganese salt total amount.
In described step (1), described precipitant is the mixing of one or more of ammonia, carbamide, citric acid or oxalic acid
Thing；The total moles of the addition of described precipitant and described nickel salt, cobalt salt and manganese salt (ni+co+mn) ratio is for 1:2-3.
In described step (1), the mol ratio of described nickel salt, cobalt salt and manganese salt is 10-20:3-5:1-3；Described nickel salt is sulfur
At least one in sour nickel, nickel nitrate or Nickel dichloride.；Described cobalt salt is at least one in cobaltous sulfate, cobalt nitrate or cobaltous chloride；
Described manganese salt is at least one in manganese nitrate or manganese sulfate.
In described step (2), the condition of described high temperature sintering step is: controls sintering temperature 300-1000 DEG C, during sintering
Between 5-30h, control air inflow 15-50m3/ h, capacity 15-50m3/ h, controls sintering furnace oxygen content 0-100%, sinters furnace pressure 0-
150pa.
In described step (2), the addition of described lithium salts is li:(ni+co+mn) mol ratio is 1-2:1；Described lithium salts is
At least one in Lithium hydrate, Quilonorm (SKB), lithium oxalate or lithium carbonate.
In described step (3), described metal salt agent is one of al salt, mg salt, ti salt, la salt, be salt or several
The mixture planted, mole addition of described metal salt agent and described lithium salts, nickel salt, cobalt salt, manganese salt total mole number (li+
Ni+co+mn ratio) is 1:2-4.
Described volatile organic solvent is preferably ethanol.
In described step (3), the temperature of described heat treatment step is 600-700 DEG C.
In described step (1), also include the step adding ionic liquid activating agent in described mixing salt solution；Described from
Sub- liquid active agent is 1- methyl -3-N-morpholinopropanesulfonic acid imidazole bisulfate, and the addition of described ionic liquid activating agent accounts for described nickel
The 0.2-0.5wt% of salt, cobalt salt and manganese salt total amount.
The invention also discloses the long circulating high-capacity lithium battery positive electrode being obtained by described preparation method.
Long circulating high-capacity lithium battery positive electrode of the present invention is ternary lithium-nickel-manganese-cobalt positive electrode, using existing common
The sedimentation method are combined with high temperature solid-state method, first with add precipitant and catalyst performance, obtain have meso-hole structure,
There is the persursor material of large specific surface area, then pass through the high-sintering process optimizing, the positive pole material of prepared stable performance
Material, then it is aided with the modification of metal salt agent, obtain a kind of specific capacity height, cycle performance is excellent, material is uniform, stability
Good tertiary cathode material.
More excellent, the method preparing long circulating high-capacity lithium battery positive electrode of the present invention, utilizing co-precipitation side
During method prepares presoma, add specific ionic liquid activating agent and carry out activation optimization, further improve obtained
The performance of positive electrode, contributes to being lifted capacity and the cycle performance of battery.
Brief description
In order that present disclosure is more likely to be clearly understood, specific embodiment below according to the present invention simultaneously combines
Accompanying drawing, the present invention is further detailed explanation, wherein,
Fig. 1 is the performance detection curve of made circulating battery 500 times in embodiment 7.
Specific embodiment
Embodiment 1
Described in the present embodiment, the preparation method of long circulating high-capacity lithium battery positive electrode, comprises the steps:
(1) prepare presoma: the mol ratio according to 10:5:1 takes nickel sulfate (10mol), cobalt nitrate (5mol) and manganese sulfate
(1mol) make metal mixed saline solution (control metal ion total concentration is 1mol/l)；And add account for described nickel salt, cobalt salt and
The Graphene of manganese salt gross mass 0.5wt% is catalyst, standby；
Take and be dissolved in water with described nickel salt, cobalt salt and manganese salt total mole number than the carbamide (8mol) for 1:2, make 1mol/l's
Urea liquid, is precipitant solution；
With the flow velocity of 10ml/min, described precipitant solution is instilled water-soluble to described metal mixed salt with dosing pump simultaneously
Carry out precipitation in liquid, control blade linear velocity 30m/s to carry out machinery compounding, after liquid to be precipitated is added completely into, normal temperature and pressure
Under, continue stirring reaction, to be precipitated terminate when not being further added by react, be precipitated reactant；Above-mentioned precipitation thing is carried out
After solid-liquid separation, it is washed with deionized repeatedly, is filtered to remove filtrate, filtrate is placed in baking oven, vacuum is done at 100 DEG C
Dry to constant weight, obtain the positive electrode material precursor of drying；
(2) prepare positive electrode: in step (1) be obtained described positive electrode material precursor in add with described nickel salt,
Cobalt salt and manganese salt total mole number are than li:(ni+co+mn) Lithium hydrate (32mol) mixed grinding for 2:1 for the mol ratio, grinds all
After even, carry out high temperature sintering curing reaction, control 300 DEG C of sintering temperature, sintering time 30h, control air inflow 15m3/ h, aerofluxuss
Amount 15m3/ h, controls sintering furnace oxygen content 10%, sinters furnace pressure 20pa, obtains anode material of lithium battery；
(3) positive electrode is modified: take with described lithium salts, nickel salt, cobalt salt, manganese salt total mole number (li+ni+co+mn) ratio
Mg (no for 1:23)2Salt (24mol) modifying agent is dissolved in alcohol solvent, and adds the described positive electrode being obtained to step (2)
Middle mixing, 50 DEG C are stirred to described organic solvent evaporating completely, and in noble gases (n2) under atmosphere in 600 DEG C of high-temperature process extremely
Constant weight is dried, is crushed to particle diameter 5-15m, screening obtains final product described long circulating high-capacity lithium battery positive electrode.
Prepare button cell using the positive electrode obtained by the present embodiment, and electrical to its stable circulation performance and charge and discharge
Can be tested, be specifically comprised the following steps that
Described positive electrode is mixed according to mass ratio 8:1:1 with conductive agent acetylene black, binding agent pvdf (Kynoar)
Close uniformly, with nmp (1-Methyl-2-Pyrrolidone), this mixture is modulated into slurry, is evenly applied on aluminium foil, puts into baking oven
In, 110 DEG C of drying 3h, take out and are washed into pole piece, 85 DEG C are vacuum dried 12 hours, carry out tabletting, 85 DEG C are vacuum dried 12 hours, system
Obtain experimental cell pole piece.It is to electrode with lithium piece, electrolyte is ec (ethyl carbonate the ester)+dmc (two of 1.0mol/l lipf6
Methyl carbonic) (volume ratio 3:7) solution, barrier film is celgard2325 film, is assembled in the glove box full of argon gas atmosphere
Button cell.
Above-mentioned prepared button cell is carried out with charge-discharge performance test, control charging/discharging voltage scope is 2.8-
In 4.3v voltage range, at 25 DEG C, charging and discharging currents are 0.2c, wherein 1c=150ma/g.The ratio of electric discharge first of this button cell
Capacity is 168.132mah/g, and first charge-discharge efficiency is 93.2%.Specific discharge capacity after cycle charge-discharge 50 times is
156.605mah/g, capability retention is 93.1%；Specific discharge capacity after cycle charge-discharge 500 times is 153.336mah/g,
Capability retention is 91.2%.It can be seen that positive electrode of the present invention contributes to lifting the capacity of battery, charge-discharge performance and follows
Ring stability.
Embodiment 2
Described in the present embodiment, the preparation method of long circulating high-capacity lithium battery positive electrode, comprises the steps:
(1) prepare presoma: the mol ratio according to 20:3:3 takes nickel nitrate (20mol), cobaltous chloride (3mol) and manganese nitrate
(3mol) make metal mixed saline solution (control metal ion total concentration is 1mol/l)；And add account for described nickel salt, cobalt salt and
The carbon nanocoils of manganese salt gross mass 1wt% are catalyst, standby；
Take and be dissolved in water with described nickel salt, cobalt salt and manganese salt total mole number than the oxalic acid (13mol) for 1:2, make 1mol/l
Oxalic acid solution, be precipitant solution；
With the flow velocity of 10ml/min, described precipitant solution is instilled water-soluble to described metal mixed salt with dosing pump simultaneously
Carry out precipitation in liquid, after liquid to be precipitated is added completely into, under normal temperature and pressure, continue stirring reaction, to be precipitated when not being further added by
Terminate reaction, be precipitated reactant；Above-mentioned precipitation thing is carried out after solid-liquid separation, is washed with deionized repeatedly, mistake
Filter filtrate, filtrate is placed in baking oven, at 100 DEG C, be dried under vacuum to constant weight, obtain the positive electrode forerunner of drying
Body；
(2) prepare positive electrode: in step (1) be obtained described positive electrode material precursor in add with described nickel salt,
Cobalt salt and manganese salt total mole number are than li:(ni+co+mn) Quilonorm (SKB) (26mol) mixed grinding for 1:1 for the mol ratio, grinds uniformly
Afterwards, carry out high temperature sintering curing reaction, control 1000 DEG C of sintering temperature, sintering time 5h, control air inflow 50m3/ h, capacity
45m3/ h, controls sintering furnace oxygen content 100%, sinters furnace pressure 150pa, obtains anode material of lithium battery；
(3) positive electrode is modified: take with described lithium salts, nickel salt, cobalt salt, manganese salt total mole number (li+ni+co+mn) ratio
Becl for 1:42Salt (13mol) modifying agent is dissolved in alcohol solvent, and adds in the described positive electrode being obtained to step (2)
Mix, 50 DEG C are stirred to described organic solvent evaporating completely, and in noble gases (n2) under atmosphere in 700 DEG C of high-temperature process to dry
Dry constant weight, is crushed to particle diameter 5-15m, and screening obtains final product described long circulating high-capacity lithium battery positive electrode.
Using the positive electrode obtained by the present embodiment, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 165.237mah/g, first
Efficiency for charge-discharge is 92.8%.Specific discharge capacity after cycle charge-discharge 50 times is 153.505mah/g, and capability retention is
92.9%；Specific discharge capacity after cycle charge-discharge 500 times is 150.531mah/g, and capability retention is 91.1%.It can be seen that
Invent capacity, charge-discharge performance and the cyclical stability that described positive electrode contributes to being lifted battery.
Embodiment 3
Described in the present embodiment, the preparation method of long circulating high-capacity lithium battery positive electrode, comprises the steps:
(1) prepare presoma: the mol ratio according to 15:4:2 takes Nickel dichloride. (15mol), cobaltous sulfate (4mol) and manganese nitrate
(2mol) make metal mixed saline solution (control metal ion total concentration is 1mol/l)；And add account for described nickel salt, cobalt salt and
The CNT of manganese salt gross mass 0.8wt% is catalyst, standby；
Take and be dissolved in water with described nickel salt, cobalt salt and manganese salt total mole number than the citric acid (7mol) for 1:3, make 1mol/l
Citric acid solution, be precipitant solution；
With the flow velocity of 10ml/min, described precipitant solution is instilled water-soluble to described metal mixed salt with dosing pump simultaneously
Carry out precipitation in liquid, after liquid to be precipitated is added completely into, under normal temperature and pressure, continue stirring reaction, to be precipitated when not being further added by
Terminate reaction, be precipitated reactant；Above-mentioned precipitation thing is carried out after solid-liquid separation, is washed with deionized repeatedly, mistake
Filter filtrate, filtrate is placed in baking oven, at 100 DEG C, be dried under vacuum to constant weight, obtain the positive electrode forerunner of drying
Body；
(2) prepare positive electrode: in step (1) be obtained described positive electrode material precursor in add with described nickel salt,
Cobalt salt and manganese salt total mole number are than li:(ni+co+mn) lithium oxalate (21mol) mixed grinding for 1:1 for the mol ratio, grinds uniformly
Afterwards, carry out high temperature sintering curing reaction, control 500 DEG C of sintering temperature, sintering time 10h, control air inflow 30m3/ h, capacity
25m3/ h, controls sintering furnace oxygen content 50%, sinters furnace pressure 100pa, obtains anode material of lithium battery；
(3) positive electrode is modified: take with described lithium salts, nickel salt, cobalt salt, manganese salt total mole number (li+ni+co+mn) ratio
Alcl for 1:33Salt (14mol) modifying agent is dissolved in alcohol solvent, and adds in the described positive electrode being obtained to step (2)
Mix, 50 DEG C are stirred to described organic solvent evaporating completely, and in noble gases (n2) under atmosphere in 700 DEG C of high-temperature process to dry
Dry constant weight, is crushed to particle diameter 5-15m, and screening obtains final product described long circulating high-capacity lithium battery positive electrode.
Using the positive electrode obtained by the present embodiment, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 175.308mah/g, first
Efficiency for charge-discharge is 93.9%.Specific discharge capacity after cycle charge-discharge 50 times is 164.439mah/g, and capability retention is
93.8%；Specific discharge capacity after cycle charge-discharge 500 times is 161.809mah/g, and capability retention is 92.3%.It can be seen that
Invent capacity, charge-discharge performance and the cyclical stability that described positive electrode contributes to being lifted battery.
Embodiment 4
Described in the present embodiment, the preparation method of long circulating high-capacity lithium battery positive electrode, comprises the steps:
(1) prepare presoma: the mol ratio according to 14:4:2 takes nickel sulfate (14mol), cobalt nitrate (4mol) and manganese nitrate
(2mol) make metal mixed saline solution (control metal ion total concentration is 1mol/l)；And add account for described nickel salt, cobalt salt and
The acetylene black of manganese salt gross mass 0.6wt% is catalyst, standby；
Take and be dissolved in water with described nickel salt, cobalt salt and manganese salt total mole number than the ammonia (10mol) for 1:2, make 1mol/l
Ammonia spirit, be precipitant solution；
With the flow velocity of 10ml/min, described precipitant solution is instilled water-soluble to described metal mixed salt with dosing pump simultaneously
Carry out precipitation in liquid, after liquid to be precipitated is added completely into, under normal temperature and pressure, continue stirring reaction, to be precipitated when not being further added by
Terminate reaction, be precipitated reactant；Above-mentioned precipitation thing is carried out after solid-liquid separation, is washed with deionized repeatedly, mistake
Filter filtrate, filtrate is placed in baking oven, at 100 DEG C, be dried under vacuum to constant weight, obtain the positive electrode forerunner of drying
Body；
(2) prepare positive electrode: in step (1) be obtained described positive electrode material precursor in add with described nickel salt,
Cobalt salt and manganese salt total mole number are than li:(ni+co+mn) lithium oxalate (40mol) mixed grinding for 2:1 for the mol ratio, grinds uniformly
Afterwards, carry out high temperature sintering curing reaction, control 800 DEG C of sintering temperature, sintering time 12h, control air inflow 40m3/ h, capacity
30m3/ h, controls sintering furnace oxygen content 0%, sinters furnace pressure 0pa, obtains anode material of lithium battery；
(3) positive electrode is modified: take with described lithium salts, nickel salt, cobalt salt, manganese salt total mole number (li+ni+co+mn) ratio
Ticl for 1:32Salt (20mol) modifying agent is dissolved in alcohol solvent, and adds in the described positive electrode being obtained to step (2)
Mix, 40 DEG C are stirred to described organic solvent evaporating completely, and in noble gases (n2) under atmosphere in 650 DEG C of high-temperature process to dry
Dry constant weight, is crushed to particle diameter 5-15m, and screening obtains final product described long circulating high-capacity lithium battery positive electrode.
Using the positive electrode obtained by the present embodiment, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 162.452mah/g, first
Efficiency for charge-discharge is 93.2%.Specific discharge capacity after cycle charge-discharge 50 times is 151.567mah/g, and capability retention is
93.3%；Specific discharge capacity after cycle charge-discharge 500 times is 148.643mah/g, and capability retention is 91.5%.It can be seen that
Invent capacity, charge-discharge performance and the cyclical stability that described positive electrode contributes to being lifted battery.
Embodiment 5
With embodiment 1, its difference only exists the preparation method of long circulating high-capacity lithium battery positive electrode described in the present embodiment
In, also include in described step (1) in described metal mixed saline solution add account for described nickel salt, cobalt salt and manganese salt total amount
The step of the ionic liquid activating agent of 0.2wt%.
Ionic liquid activating agent described in the present embodiment is 1- methyl -3-N-morpholinopropanesulfonic acid imidazole bisulfate, is that prior art is produced
Product, commercially available commercially available prod or prepare according to existing conventional method, the 1- methyl -3-N-morpholinopropanesulfonic acid adopting in the present embodiment
The synthesis of imidazole bisulfate schematically as follows, and prepares in accordance with the following steps:
Weigh 18.4g PS, and measure 100ml ethyl acetate and add in there-necked flask, load onto constant voltage and drip
Liquid funnel, magnetic stirring apparatuss and reflux condensing tube, are slowly added to 12.3g n- methyl when being heated to 60 DEG C in water-bath
Imidazoles, after being added dropwise to complete, makes architecture heat preservation react 2h at 70-80 DEG C, to generation white precipitate；Carry out decompression to system to take out
Filter, and wash filter cake with ethyl acetate, put into 100 DEG C of drying in oven, products obtained therefrom is 1- (3- sulfonic group) propyl group -3- methyl
Imidazole salts (mim-ps)；
Weigh 20.4g mim-ps to add in 250ml there-necked flask, add water and so that it is completely dissolved, will under magnetic agitation
6.1ml concentrated sulphuric acid is slowly added in flask, after being added dropwise to complete, is warming up to 90 DEG C and continues reaction 2h, then with rotation in water-bath
Turn the moisture that evaporimeter removes in reaction system, obtain faint yellow sticky shape product liquid, as required 1- methyl -3- the third sulphur
Imidazole acid hydrogen sulphate ionic liquid catalyst.
Using the positive electrode obtained by the present embodiment, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 185.178mah/g, first
Efficiency for charge-discharge is 95.7%.Specific discharge capacity after cycle charge-discharge 50 times is 177.401mah/g, and capability retention is
95.8%；Specific discharge capacity after cycle charge-discharge 500 times is 175.364ah/g, and capability retention is 94.7%, cyclic curve
Change is less, and charge-discharge performance is stable.Simultaneously because the modifying function of ionic liquid activating agent, it is more conducive to improve made battery
Capacity, charge-discharge performance and cycle performance of battery.
Embodiment 6
With embodiment 2, its difference only exists the preparation method of long circulating high-capacity lithium battery positive electrode described in the present embodiment
In, also include in described step (1) in described metal mixed saline solution add account for described nickel salt, cobalt salt and manganese salt total amount
The step of the ionic liquid activating agent of 0.5wt%.
Ionic liquid activating agent described in the present embodiment is 1- methyl -3-N-morpholinopropanesulfonic acid imidazole bisulfate, and its preparation method is same
Embodiment 5.
Using the positive electrode obtained by the present embodiment, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 184.362mah/g, first
Efficiency for charge-discharge is 95.5%.Specific discharge capacity after cycle charge-discharge 50 times is 177.909mah/g, and capability retention is
96.5%；Specific discharge capacity after cycle charge-discharge 500 times is 175.212ah/g, and capability retention is 95.03%, and circulation is bent
Line change is less, and charge-discharge performance is stable.Simultaneously because the modifying function of ionic liquid activating agent, it is more conducive to improve made electricity
The capacity in pond, charge-discharge performance and cycle performance of battery.
Embodiment 7
With embodiment 3, its difference only exists the preparation method of long circulating high-capacity lithium battery positive electrode described in the present embodiment
In, also include in described step (1) in described metal mixed saline solution add account for described nickel salt, cobalt salt and manganese salt total amount
The step of the ionic liquid activating agent of 0.4wt%.
Ionic liquid activating agent described in the present embodiment is 1- methyl -3-N-morpholinopropanesulfonic acid imidazole bisulfate, and its preparation method is same
Embodiment 5.
Using the positive electrode obtained by the present embodiment, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 189.317mah/g, first
Efficiency for charge-discharge is 96.4%.Specific discharge capacity after cycle charge-discharge 50 times is 182.691mah/g, and capability retention is
96.5%；Specific discharge capacity after cycle charge-discharge 500 times is 180.04ah/g, and capability retention is 95.1%, gives in accompanying drawing 1
Go out the cycle performance detection curve of described battery it is seen that cyclic curve change is less, charge-discharge performance is stable.Simultaneously because from
The modifying function of sub- liquid active agent, is more conducive to improve capacity, charge-discharge performance and the cycle performance of battery of made battery.
Embodiment 8
With embodiment 4, its difference only exists the preparation method of long circulating high-capacity lithium battery positive electrode described in the present embodiment
In, also include in described step (1) in described metal mixed saline solution add account for described nickel salt, cobalt salt and manganese salt total amount
The step of the ionic liquid activating agent of 0.3wt%.
Ionic liquid activating agent described in the present embodiment is 1- methyl -3-N-morpholinopropanesulfonic acid imidazole bisulfate, and its preparation method is same
Embodiment 5.
Using the positive electrode obtained by the present embodiment, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 181.328mah/g, first
Efficiency for charge-discharge is 95.5%.Specific discharge capacity after cycle charge-discharge 50 times is 172.624mah/g, and capability retention is
95.2%；Specific discharge capacity after cycle charge-discharge 500 times is 170.63ah/g, and capability retention is 94.1%, cyclic curve
Change is less, and charge-discharge performance is stable.Simultaneously because the modifying function of ionic liquid activating agent, it is more conducive to improve made battery
Capacity, charge-discharge performance and cycle performance of battery.
Comparative example 1
Respectively with embodiment 1, it differs only in the preparation method of anode material of lithium battery described in this comparative example, described step
Suddenly in (1), without catalyst described in each embodiment.
Using the positive electrode obtained by this comparative example, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 142.109mah/g, first
Efficiency for charge-discharge is 90.1%.Specific discharge capacity after cycle charge-discharge 50 times is 128.182mah/g, and capability retention is
90.2%；Specific discharge capacity after cycle charge-discharge 500 times is 114.824mah/g, and capability retention is 80.8%.Comparative example 2
Respectively with embodiment 2, it differs only in the preparation method of anode material of lithium battery described in this comparative example, described step
Suddenly in (1), without catalyst described in each embodiment.
Using the positive electrode obtained by this comparative example, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 138.712mah/g, first
Efficiency for charge-discharge is 90.2%.Specific discharge capacity after cycle charge-discharge 50 times is 125.257mah/g, and capability retention is
90.3%；Specific discharge capacity after cycle charge-discharge 500 times is 111.247mah/g, and capability retention is 80.2%.Comparative example 3
Respectively with embodiment 3, it differs only in the preparation method of anode material of lithium battery described in this comparative example, described step
Suddenly in (1), without catalyst described in each embodiment.
Using the positive electrode obtained by this comparative example, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 142.255mah/g, first
Efficiency for charge-discharge is 90.8%.Specific discharge capacity after cycle charge-discharge 50 times is 128.883mah/g, and capability retention is
90.6%；Specific discharge capacity after cycle charge-discharge 500 times is 117.36mah/g, and capability retention is 82.5%.Comparative example 4
Respectively with embodiment 4, it differs only in the preparation method of anode material of lithium battery described in this comparative example, described step
Suddenly in (1), without catalyst described in each embodiment.
Using the positive electrode obtained by this comparative example, prepare button cell according to method in embodiment 1, and it is circulated
Stability and charge-discharge performance are tested.Control charging/discharging voltage scope to be in 2.8-4.3v voltage range, fill at 25 DEG C
Discharge current is 0.2c, wherein 1c=150ma/g.The first discharge specific capacity of this button cell is 141.732mah/g, first
Efficiency for charge-discharge is 90.4%.Specific discharge capacity after cycle charge-discharge 50 times is 128.267mah/g, and capability retention is
90.5%；Specific discharge capacity after cycle charge-discharge 500 times is 115.795mah/g, and capability retention is 81.7%.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.Right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need to be exhaustive to all of embodiment.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (10)
1. a kind of preparation method of long circulating high-capacity lithium battery positive electrode is it is characterised in that comprise the steps:
(1) prepare presoma: take nickel salt, cobalt salt and manganese salt to make mixing salt solution, add catalyst and precipitant mixes, go forward side by side
Row precipitation；To be precipitated be not further added by, filter taking precipitate washed, remove filtrate and drying, before obtaining final product positive electrode
Drive body；
(2) prepare positive electrode: add lithium salt in described positive electrode material precursor, after grinding uniformly, carry out height
Warm sintering curing reaction, obtains positive electrode；
(3) positive electrode is modified: takes slaine modifying agent to be dissolved in volatile organic solvent, and adds described positive electrode to mix
Even, to described organic solvent evaporating completely, high-temperature heat treatment is to dry, pulverize screening under inert gas atmosphere for high-temperature stirring,
Obtain final product described long circulating high-capacity lithium battery positive electrode.
2. the preparation method of long circulating high-capacity lithium battery positive electrode according to claim 1 is it is characterised in that described
In step (1), described catalyst is the mixture of one or more of Graphene, CNT, carbon nanocoils or acetylene black；
The addition of described catalyst accounts for the 0.5-1wt% of described nickel salt, cobalt salt and manganese salt total amount.
3. long circulating high-capacity lithium battery positive electrode according to claim 1 and 2 preparation method it is characterised in that
In described step (1), described precipitant is the mixture of one or more of ammonia, carbamide, citric acid or oxalic acid；Described heavy
The total moles of the addition of shallow lake agent and described nickel salt, cobalt salt and manganese salt (ni+co+mn) ratio is for 1:2-3.
4. the preparation method of long circulating high-capacity lithium battery positive electrode according to claim 3 is it is characterised in that described
In step (1), the mol ratio of described nickel salt, cobalt salt and manganese salt is 10-20:3-5:1-3；Described nickel salt is nickel sulfate, nickel nitrate
Or at least one in Nickel dichloride.；Described cobalt salt is at least one in cobaltous sulfate, cobalt nitrate or cobaltous chloride；Described manganese salt is nitre
At least one in sour manganese or manganese sulfate.
5. the preparation method of the long circulating high-capacity lithium battery positive electrode according to any one of claim 1-4, its feature
It is, in described step (2), the condition of described high temperature sintering step is: control sintering temperature 300-1000 DEG C, sintering time 5-
30h, controls air inflow 15-50m3/ h, capacity 15-50m3/ h, controls sintering furnace oxygen content 0-100%, sinters furnace pressure 0-
150pa.
6. the preparation method of long circulating high-capacity lithium battery positive electrode according to claim 5 is it is characterised in that described
In step (2), the addition of described lithium salts is li:(ni+co+mn) mol ratio is 1-2:1；Described lithium salts is Lithium hydrate, second
At least one in sour lithium, lithium oxalate or lithium carbonate.
7. the preparation method of the long circulating high-capacity lithium battery positive electrode according to any one of claim 1-6, its feature
It is, in described step (3), described metal salt agent is one or more of al salt, mg salt, ti salt, la salt, be salt
Mixture, mole addition of described metal salt agent and described lithium salts, nickel salt, cobalt salt, manganese salt total mole number (li+ni+co
+ mn) ratio be 1:2-4.
8. the preparation method of long circulating high-capacity lithium battery positive electrode according to claim 7 is it is characterised in that described
In step (3), the temperature of described heat treatment step is 600-700 DEG C.
9. the preparation method of the long circulating high-capacity lithium battery positive electrode according to any one of claim 1-8, its feature
It is, in described step (1), also include the step adding ionic liquid activating agent in described mixing salt solution；Described ion
Liquid active agent is 1- methyl -3-N-morpholinopropanesulfonic acid imidazole bisulfate, the addition of described ionic liquid activating agent account for described nickel salt,
Cobalt salt and the 0.2-0.5wt% of manganese salt total amount.
10. the long circulating high-capacity lithium battery positive electrode that preparation method described in any one of claim 1-9 obtains.
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