CN107978752A - A kind of high security lithium ion positive electrode for battery material and preparation method thereof - Google Patents
A kind of high security lithium ion positive electrode for battery material and preparation method thereof Download PDFInfo
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- CN107978752A CN107978752A CN201711243044.7A CN201711243044A CN107978752A CN 107978752 A CN107978752 A CN 107978752A CN 201711243044 A CN201711243044 A CN 201711243044A CN 107978752 A CN107978752 A CN 107978752A
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- 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 discloses a kind of high security lithium ion positive electrode for battery material and preparation method thereof, the preparation method includes the following steps：(1) parameter such as pH and ammonia value by controlling forerunner's precursor reactant, synthesize a kind of presoma with long sheet whisker morphology, by adding the one or more in the elements such as Zr, Mg, Al, Ti, Ce, Er during synthesis, to stablize the structure of presoma；(2) presoma and a certain proportion of lithium source mixed sintering are obtained into the nickel-cobalt lithium manganate cathode material with monocrystalline pattern to be covered；(3) by the method for mixed at high speed, cladding of the LiFePO4 to nickle cobalt lithium manganate is completed.Overall modifying process of the invention is easy to operate, it is easy to implement in process of production, the composite positive pole finally obtained has good cycle performance and heat endurance, can meet the making demand of square, cylinder and soft-package battery, can be applied to the fields such as electric automobile, energy-accumulating power station.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of high security lithium ion positive electrode for battery material
And preparation method thereof.
Background technology
Nickel-cobalt lithium manganate cathode material is widely used in number with the advantages that its battery specific energy density is high, occupancy is small
3C and electric passenger vehicle field, but due to that side reaction can occur with electrolyte in charge and discharge process, cause the change of material structure
Change, cause the thermal stability of material to be deteriorated, so as to limit its application in electric motor coach field.
At present, conventional modified technique on nickel-cobalt lithium manganate material surface mainly by coating one layer of oxide or phosphoric acid
Salt realizes the lifting of performance.Research shows that Phosphate coating is coated on the cyclical stability for improving material, multiplying power compared with oxide
Significant effect in terms of performance and heat endurance, this is because phosphate ratio oxide has more preferable lithium ion mobility ability and electricity
Sub- transmission capacity, further reduces diffusion impedance and ohmage.And it is oxide coated, in initial charge and discharge cycles process
In stablize relatively, but in the case of high voltage or prolonged contact electrolyte, its chemical property can become unstable.
LiFePO4Material has good cycle performance and heat endurance, on a large scale should in electric motor coach field at present
With, such as the LiFePO4 electric bus of BYD, but specific energy density due to battery and voltage platform are relatively low, serious shadow
The course continuation mileage of electric automobile is rung, is limited in passenger car use aspect.Therefore, by the high nickel-cobalt lithium manganate material of specific energy density
As kernel, by the good LiFePO of cycle performance and heat endurance4Covering material of the material as outer layer, makes full use of the two
Advantage, improves the cycle performance and heat endurance of ternary material, obtains a kind of energy density height, the composite wood having a safety feature
Material.
Many disclosed patents and document have been proposed improving material in nickel-cobalt lithium manganate material surface coated phosphate
Expect the method for security performance.
Document (W.S.Kim, S.B.Kim, I.C.Jang, et al..Remarkable improvement in cell
safety for Li[Ni0.5Co0.2Mn0.3]O2coated with LiFePO4.Journal of Alloys and
Compounds, 2010 (492)：L87~L90) it have studied the Li [Ni for coating 1.5wt% LiFePO4s0.5Co0.2Mn0.3]O2It is high
Multiplying power discharging and overcharge, cross hot property.Under 20C current ratios, highly stable put is shown with battery prepared by the material
Electrical property；When 18V overcharges test, LiFePO is coated4Li [Ni0.5Co0.2Mn0.3]O2Material surface temperature is by original 140 DEG C
Drop to 60 DEG C.
Patent publication No. (CN103825001A) have studied nickle cobalt lithium manganate and cobalt acid lithium surface coats one layer of ferrous iron
The security performance of compound improves.By cladding, two phase structure is obtained, reduces cathode during lithium rechargeable battery charge/discharge
Current potential, while because reproducibility Fe (II) and its compound exist, possess the characteristic of trapping highly reactive form of oxygen atom immediately, in not shadow
While ringing energy density demand, the cells burst brought by electrolyte decomposition and positive electrode oxygen release and explosion are reduced or suppressed
Risk.
Patent publication No. (CN105406069A) have studied shadow of the lithium ferric manganese phosphate cladding to nickle cobalt lithium manganate security performance
Ring.Main technique is to synthesize one layer of lithium ferric manganese phosphate in nickle cobalt lithium manganate surface in situ, utilizes the faintly acid of lithium ferric manganese phosphate, drop
Low nickle cobalt lithium manganate surface residual alkali, improves storage and homogenate technique；Using the high voltage platform and heat endurance of lithium ferric manganese phosphate,
Overcharge resistance performance energy is lifted, reduces battery core aerogenesis, improves security performance.
Patent publication No. (CN104577093A) have studied lithium ferric manganese phosphate cladding to nickel cobalt lithium aluminate (NCA) security performance
Influence.The technique coated using dry method, technique is simple, will not significantly reduce compacting, ensures security performance.
Patent publication No. (CN103474625A) synthesizes one layer of phosphorus using sol-gal process in nickle cobalt lithium manganate surface in situ
Sour iron lithium.The Ni contents on surface can be reduced in the ferric phosphate lithium layer that positive electrode surface is formed, reduce the generation of side reaction, are lifted
The heat endurance of material.Nickel manganese element can be complexed with the organic principle in colloidal sol, formed weak chemical bond effect, realized the equal of material
Even cladding.
The patent of research LiFePO4 cladding nickle cobalt lithium manganate is more based on surface in situ synthesizing iron lithium phosphate above, method
Complex, the purity of LiFePO4 is also difficult to ensure that, and with the patent of LiFePO4 finished product cladding nickle cobalt lithium manganate, by preceding
It is less to drive the narration that bodily form looks improve to lift nickle cobalt lithium manganate heat endurance；In addition, when carrying out LiFePO4 cladding, nickel cobalt
LiMn2O4 selects the material that pattern is secondary ball more.
The content of the invention
The technical problems to be solved by the invention are to overcome the technological deficiency of background technology, there is provided a kind of high security lithium from
Sub- positive electrode for battery material and preparation method thereof.The present invention utilizes three aspects such as precursor doped, whisker control and surface cladding
Technology, to lift the heat endurance of nickel-cobalt lithium manganate material and security performance；Overall modifying process of the invention is easy to operate,
Easy to implement in production process, the composite positive pole finally obtained has good cycle performance and heat endurance, can meet
The making demand of square, cylinder and soft-package battery, can be applied to the fields such as electric automobile, energy-accumulating power station.
Technological means is used by the present invention solves above-mentioned technical problem：
A kind of preparation method of high security lithium ion positive electrode for battery material, the high security lithium ion battery is with just
The chemical formula of pole material is LiNixCoyMnzN(1-x-y-z)O2@LiFePO4, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ z ＜ 1, x+y+z in formula
Any one or more in ＜ 1, N Zr, Mg, Al, Ti, Ce, Er element.
The preparation method of the high security lithium ion positive electrode for battery material, includes the following steps：
(1) doping metals N salt is dissolved in deionized water and is configured to solution A, by soluble nickel salt, cobalt salt and manganese salt press than
Example is configured to mixing salt solution B, and nickel, cobalt, the ratio of manganese and N element are x: y: z: (1-x-y-z), 0 ＜ x ＜, 1,0 ＜ y ＜ in formula
1,0 ＜ z ＜ 1, x+y+z ＜ 1；Aqueous slkali and enveloping agent solution are prepared respectively；The doping metals N salt is to contain metallic element N
Soluble compound, the N be Zr, Mg, Al, Ti, Ce, Er element in any one or more；
(2) it is step (1) solution A, the mixing salt solution B, the aqueous slkali and the enveloping agent solution is independent
It is pumped into reaction kettle and is stirred, mixing speed is 100~800rpm, controls the flow velocity of aqueous slkali and enveloping agent solution and makes to mix
It is 9~13 to close solution ph, and temperature of reaction kettle is controlled at 30~90 DEG C, and whole process is passed through inert gas shielding；Treat that step (1) is described
Mixing salt solution B continues to stir after all adding reaction kettle, and overflow to aging reactor is aged 5~36h, is then filtered by centrifuge
Separation, washing, 6~24h is finally dried at 80~200 DEG C, obtains nickel cobalt manganese hydroxide precursor；
(3) step (2) the nickel cobalt manganese hydroxide precursor is mixed in proportion with lithium source, at 700~1100 DEG C
6~20h is calcined, 200~400 mesh sieves is crossed after broken two pairs of rollers, obtains nickle cobalt lithium manganate C to be covered；
(4) step (3) the nickle cobalt lithium manganate C is weighed in proportion with LiFePO4, is mixed, gone out by high-speed mixer
Expect 200~400 mesh sieves, and obtain high security lithium ion positive electrode for battery material.
Preferably, in the step (1), the doping metals N salt is the soluble compound containing metallic element N, institute
It is any one or more in Zr, Mg, Al, Ti, Ce, Er element to state N, and the Zr is zirconium sulfate, in zirconium nitrate, zirconium chloride
Any one, the Mg is any one in magnesium chloride, magnesium sulfate, magnesium nitrate, and the Al is aluminum nitrate, aluminium chloride, sulfuric acid
Any one in aluminium, the Ti are titanium sulfate or Titanium Nitrate, and the Ce is cerium chloride, and the Er is erbium nitrate, erbium sulfate, chlorine
Change any one in erbium.
Preferably, in the step (1), the nickel salt is nickel chloride, nickel sulfate, in nickel nitrate any one or it is more
Kind；The cobalt salt is any one or more in cobalt chloride, cobaltous sulfate, cobalt nitrate；The manganese salt for manganese chloride, manganese sulfate,
Any one or more in manganese nitrate.
Preferably, in the step (1), the aqueous slkali is any one or more in NaOH, KOH, LiOH solution,
Concentration is 1~10mol/L；The enveloping agent solution is ammonium hydroxide, appointing in ammonium citrate, ammonium nitrate, ammonium sulfate, ammonium chloride solution
Meaning is one or more, and concentration is 1~10mol/L.
Preferably, in the step (2), the inert gas is one or both of nitrogen or argon gas.
Preferably, in the step (2), the nickel cobalt manganese hydroxide precursor pattern is long sheet.
Preferably, in the step (3), the lithium source is lithium carbonate, any in lithium hydroxide, lithium acetate, lithium oxalate
It is one or more.
Preferably, in the step (3), the additive amount of the lithium source accounts for the 40 of nickel cobalt manganese hydroxide precursor gross mass
~50%.
Preferably, in the step (3), the D50 of the nickle cobalt lithium manganate C to be covered is 3~20 μm, and pattern is monocrystalline
Particle.
Preferably, in the step (4), the primary particle size of the LiFePO4 is 50~500nm.
Preferably, in the step (4), the ratio that the LiFePO4 accounts for positive electrode is 1~30%, and top layer coats
There is carbon.
Preferably, in the step (4), the revolution of the high-speed mixer is 500~3000rpm, incorporation time for 5~
30min。
Present invention also offers a kind of lithium ion battery, the positive electrode of the lithium ion battery is above-mentioned technical proposal institute
A kind of Gao An is prepared in a kind of high security lithium ion positive electrode for battery material stated, or method described in above-mentioned technical proposal
Full property anode material for lithium ion battery.
The basic principle of the present invention：
The present invention mainly coats one layer of LiFePO4 to realize by the modification to precursor of nickel-cobalt-lithium-manganese-oxide and surface；This
Invention is first by being prepared the doping type presoma of long sheet, and then the positive electrode of monocrystalline pattern is prepared, finally
Cladding LiFePO is prepared4Ternary material；The present invention by control the process conditions such as pH value and revolution in reaction kettle come
A kind of presoma with long sheet whisker morphology is synthesized, during driving body before the synthesis, the complexing of element is doped, makes
Effect must be adulterated to be more uniformly distributed；The present invention is during presoma prepares positive electrode, by controlling sintering temperature so that burns
The positive electrode presentation monocrystalline pattern born, and non-agglomerated secondary ball material；The present invention is high by controlling when being coated
The revolution and incorporation time of fast mixer so that cladding is more uniformly distributed.
Compared with prior art, technical scheme has the following advantages that：
(1) present invention is using tripartite's surface technologies such as precursor doped, whisker control and surface claddings, to lift nickel cobalt mangaic acid
The heat endurance and security performance of lithium material；
(2) present invention is while nickel cobalt manganese element is complexed, by being complexed doped chemical, it is ensured that doped chemical mixes
Inside presoma, more uniformly spread；
(3) present invention uses pattern to be sintered for the presoma of long sheet, and sintering finished pattern is single crystal grain, itself
Increase in terms of more secondary ball particle heat endurance；
(4) present invention is coated using LiFePO4, with reference to the characteristic of two kinds of materials, in the not significantly reduced feelings of guaranteed capacity
Under condition, the heat endurance and security performance of material are significantly lifted.
(5) the overall modifying process of the present invention is easy to operate, easy to implement in process of production, finally obtain it is compound just
Pole material has good cycle performance and heat endurance, can meet the making demand of square, cylinder and soft-package battery, can apply
In fields such as electric automobile, energy-accumulating power stations.
Brief description of the drawings
Fig. 1 is the SEM for the mixing Mg type nickel cobalt manganese hydroxide precursors figures that the embodiment of the present invention 1 prepares gained；
Fig. 2 is the SEM figures for the high security lithium ion positive electrode for battery material that the embodiment of the present invention 1 prepares gained；
Fig. 3 prepares the button battery of the high security lithium ion positive electrode for battery material of gained for the embodiment of the present invention 1 first
Charging and discharging curve；
Fig. 4 is 1C times of the full battery for the high security lithium ion positive electrode for battery material that the embodiment of the present invention 1 prepares gained
25 DEG C of cyclic curves of rate discharge and recharge；
Fig. 5 is the high security lithium ion positive electrode for battery material that the embodiment of the present invention 1 and comparative example 1 prepare gained
DSC curve.
Embodiment
Content for a better understanding of the present invention, is described further with reference to specific embodiments and the drawings.Ying Li
Solution, these embodiments are only used for that the present invention is further described, rather than limit the scope of the invention.In addition, it should also be understood that,
After having read present disclosure, person skilled in art makes the present invention some nonessential changes or adjustment, still belongs to
In protection scope of the present invention.
Comparative example 1
(1) magnesium sulfate is weighed in proportion and is dissolved in deionized water preparation Adlerika, by nickel sulfate, cobaltous sulfate and manganese sulfate
Mixing salt solution is configured in proportion, wherein, the gross weight of solute is 500kg, and nickel, cobalt, the molar ratio of manganese and magnesium elements are 0.5
∶0.2∶0.295∶0.005；The sodium hydroxide solution of 5mol/L and the ammonia spirit of 5mol/L are prepared respectively；
(2) by step (1) Adlerika, the nickel cobalt manganese mixing salt solution, the sodium hydroxide solution and institute
State ammonia spirit to be individually pumped into reaction kettle and be stirred, mixing speed 500rpm, control sodium hydroxide solution and ammonium hydroxide
The flow velocity of solution makes mixed solution pH value be 11, is judged by observing sphericity and the pattern of presoma, it is ensured that pattern is length
Sheet, at 55 DEG C, reaction kettle whole process is passed through nitrogen protection for temperature of reaction kettle control；The mixing salt solution to be prepared all adds
Continue to stir after entering reaction kettle, final overflow to aging reactor is aged 24h, is then separated by filtration by centrifuge, washs, finally exists
12h is dried at 150 DEG C, obtains required mixing Mg type nickel cobalt manganese hydroxide precursors；
(3) step (2) the nickel cobalt manganese hydroxide precursor is taken out into 30kg, passes through inclined ball milling with 14kg lithium carbonates
Machine is uniformly mixed, and estimates no white point, and 16h is calcined at 950 DEG C, and 400 mesh sieves are crossed after broken two pairs of rollers, obtains the nickel that D50 is 6 μm
Cobalt manganic acid lithium positive electrode, pattern are single crystal grain；
Electrical testing 4.2V is detained by CR2430, battery 0.1C discharge capacities are 160mAh/g；053048 full battery testing
4.2V, battery 1C capacity 149mAh/g, 300 room temperature follow (the loop test condition of capacity retention ratio more than 94%：1C/1C charge and discharges,
Similarly hereinafter), 300 45 DEG C of high temperature circulation capacity retention ratios more than 92%, acupuncture and overcharge in 4 batteries, and 3 by the way that 1 does not lead to
Cross, full electricity DSC tests 177.06 DEG C of exothermic temperature of starting, peak heat release temperature is 279.13 DEG C.
Embodiment 1
(1) magnesium sulfate is weighed in proportion and is dissolved in deionized water preparation Adlerika, by nickel sulfate, cobaltous sulfate and manganese sulfate
Mixing salt solution is configured in proportion, wherein, the gross weight of solute is 500kg, and nickel, cobalt, the ratio of manganese and magnesium elements are 0.5:
0.2∶0.295∶0.005；The sodium hydroxide solution of 5mol/L and the ammonia spirit of 5mol/L are prepared respectively；
(2) by step (1) Adlerika, the nickel cobalt manganese mixing salt solution, the sodium hydroxide solution and institute
State ammonia spirit to be individually pumped into reaction kettle and be stirred, mixing speed 500rpm, control sodium hydroxide solution and ammonium hydroxide
The flow velocity of solution makes mixed solution pH value be 11, is judged by observing sphericity and the pattern of presoma, it is ensured that pattern is length
Sheet, at 55 DEG C, reaction kettle whole process is passed through nitrogen protection for temperature of reaction kettle control；The mixing salt solution to be prepared all adds
Continue to stir after entering reaction kettle, final overflow to aging reactor is aged 24h, is then separated by filtration by centrifuge, washs, finally exists
12h is dried at 150 DEG C, obtain required mixing Mg type nickel cobalt manganese hydroxide precursors (see Fig. 1)；
(3) step (2) the nickel cobalt manganese hydroxide precursor is taken out into 30kg, passes through inclined ball milling with 14kg lithium carbonates
Machine is uniformly mixed, and estimates no white point, and 16h is calcined at 950 DEG C, 400 mesh sieves are crossed after broken two pairs of rollers, obtains D50 and be 6 μm treating
The nickle cobalt lithium manganate of cladding, pattern are single crystal grain；
(4) step (3) nickle cobalt lithium manganate to be covered is taken out 17.5kg and 2.5kg primary particle sizes is
The LiFePO4 of 200nm mixes 25min in high-speed mixer, revolution 1500rpm, and when discharging crosses 400 mesh sieves, obtains Gao An
Full property anode material for lithium ion battery (see Fig. 2).
Electrical testing 4.2V is detained by CR2430, battery 0.1C discharge capacities are 159mAh/g, and first charge-discharge curve shows
For Double tabletop (see Fig. 3)；053048 full battery testing 4.2V, battery 1C capacity 146mAh/g, 300 times room temperature follows capacity retention ratio
More than 96% (see Fig. 4, loop test condition：1C/1C charge and discharges, similarly hereinafter), 300 45 DEG C of high temperature circulation capacity retention ratios 94% with
On, acupuncture and 4 batteries are overcharged full by full electricity DSC originates 177.06 DEG C of exothermic temperature, exothermic peak temperature 286.35
℃.The more uncoated sample of coated LiFePO 4 for lithium ion batteries sample, capacity slightly reduce, but cycle performance and heat endurance are obviously improved.
The DSC curve for the high security lithium ion positive electrode for battery material that the present embodiment and comparative example 1 prepare gained is shown in figure
5。
Embodiment 2
(1) aluminum nitrate is weighed in proportion and is dissolved in deionized water preparation aluminum nitrate solution, by nickel nitrate, cobalt nitrate and manganese nitrate
Mixing salt solution is configured in proportion, wherein, the gross weight of solute is 500kg, and nickel, cobalt, the ratio of manganese and magnesium elements are 0.53:
0.2∶0.267∶0.003；The sodium hydroxide solution of 5mol/L and the ammonium citrate solution of 5mol/L are prepared respectively；
(2) by step (1) aluminum nitrate solution, the nickel cobalt manganese mixing salt solution, the sodium hydroxide solution and institute
State ammonium citrate solution to be individually pumped into reaction kettle and be stirred, mixing speed 600rpm, control sodium hydroxide solution and
The flow velocity of ammonium citrate solution makes mixed solution pH value be 12, and temperature of reaction kettle is controlled at 55 DEG C, and reaction kettle whole process is passed through nitrogen
Protection；Continuing to stir after the mixing salt solution prepared all adds reaction kettle, final overflow to aging reactor is aged 24h,
Then it is separated by filtration by centrifuge, washs, finally dry 18h at 120 DEG C, obtains required mixing Al type nickel cobalt manganese hydroxides
Thing presoma；
(3) step (2) the nickel cobalt manganese hydroxide precursor is taken out into 30kg, passes through inclined ball milling with 14kg lithium carbonates
Machine is uniformly mixed, and estimates no white point, and 16h is calcined at 940 DEG C, 400 mesh sieves are crossed after broken two pairs of rollers, obtains D50 and be 6 μm treating
The nickle cobalt lithium manganate of cladding, pattern are single crystal grain；
(4) it is 100nm's step (3) nickle cobalt lithium manganate to be covered to be taken out 19kg with 1kg primary particles size
LiFePO4 mixes 15min in high-speed mixer, revolution 1800rpm, and when discharging crosses 400 mesh sieves, obtains high security lithium
Ion battery positive electrode.
Electrical testing 4.2V is detained by CR2430, battery 0.1C discharge capacities are 164mAh/g；053048 full battery testing
4.2V, battery 1C capacity 148mAh/g, 300 room temperature follow (the loop test condition of capacity retention ratio more than 95%：1C/1C charge and discharges,
Similarly hereinafter), 300 45 DEG C of high temperature circulation capacity retention ratios more than 93%, acupuncture and overcharge 4 batteries full by.
Embodiment 3
(1) titanium sulfate is weighed in proportion and is dissolved in deionized water preparation titanium sulfate solution, by nickel sulfate, cobaltous sulfate and manganese sulfate
Mixing salt solution is configured in proportion, wherein, the gross weight of solute is 500kg, and nickel, cobalt, the ratio of manganese and titanium elements are 0.55:
0.2∶0.242∶0.008；The sodium hydroxide solution of 5mol/L and the ammonia spirit of 5mol/L are prepared respectively；
(2) by step (1) titanium sulfate solution, the nickel cobalt manganese mixing salt solution, the sodium hydroxide solution and institute
State ammonia spirit to be individually pumped into reaction kettle and be stirred, mixing speed 700rpm, control sodium hydroxide solution and ammonium hydroxide
The flow velocity of solution makes mixed solution pH value be 11.5, controls the flow velocity of titanium sulfate and nickel cobalt manganese salt-mixture make it that reaction is more thorough
Bottom, is judged by observing sphericity and the pattern of presoma, and temperature of reaction kettle is controlled at 55 DEG C, and reaction kettle whole process is passed through nitrogen
Protection；Continuing to stir after the mixing salt solution prepared all adds reaction kettle, final overflow to aging reactor is aged 24h,
Then it is separated by filtration by centrifuge, washs, finally dry 15h at 180 DEG C, obtains required mixing Ti type nickel cobalt manganese hydroxides
Thing presoma；
(3) step (2) the nickel cobalt manganese hydroxide precursor is taken out into 30kg, passes through inclined ball milling with 14kg lithium carbonates
Machine is uniformly mixed, and estimates no white point, and 16h is calcined at 930 DEG C, 400 mesh sieves are crossed after broken two pairs of rollers, obtains D50 and be 6 μm treating
The nickle cobalt lithium manganate of cladding, pattern are single crystal grain；
(4) it is 250nm's step (3) nickle cobalt lithium manganate to be covered to be taken out 17kg with 3kg primary particles size
LiFePO4 mixes 10min in high-speed mixer, revolution 2000rpm, and when discharging crosses 400 mesh sieves, obtains high security lithium
Ion battery positive electrode.
Electrical testing 4.2V is detained by CR2430, battery 0.1C discharge capacities are 166mAh/g；053048 full battery testing
4.2V, battery 1C capacity 151mAh/g, 300 room temperature follow (the loop test condition of capacity retention ratio more than 96%：1C/1C charge and discharges,
Similarly hereinafter), 300 45 DEG C of high temperature circulation capacity retention ratios more than 93%, acupuncture and overcharge 4 batteries full by.
The presoma pattern of long sheet as can be seen from Figure 1, Fig. 2 can be seen that the positive electrode of the monocrystalline pattern after sintering
And uniform covered effect, the DSC curve of cyclic curve and Fig. 5 from Fig. 4 can be seen that the cathode that the present invention is prepared
Material circulation and heat endurance all have greatly lifting.
From the point of view of the electrical performance data of embodiment, the heat endurance and cycle performance of the nickle cobalt lithium manganate of coated LiFePO 4 for lithium ion batteries
Uncoated material is substantially better than, capacity aspect is a kind of material of high comprehensive performance, it is believed that can close to uncoated material
To meet the making demand of square, cylinder and soft-package battery, applied to fields such as electric automobile, energy-accumulating power stations.
Described above is not the limitation to invention, and the present invention is also not limited to the example above.The common skill of the art
Art personnel are in the essential scope of invention, and the variations, modifications, additions or substitutions made should also belong to protection scope of the present invention.
Claims (10)
- A kind of 1. preparation method of high security lithium ion positive electrode for battery material, it is characterised in that the high security lithium from The chemical formula of sub- positive electrode for battery material is LiNixCoyMnzN(1-x-y-z)O2@LiFePO4, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ z in formula ＜ 1, x+y+z ＜ 1, any one or more in N Zr, Mg, Al, Ti, Ce, Er element；The preparation method of the high security lithium ion positive electrode for battery material, includes the following steps：(1) doping metals N salt is dissolved in deionized water and is configured to solution A, soluble nickel salt, cobalt salt and manganese salt are matched somebody with somebody in proportion It is made mixing salt solution B, nickel, cobalt, the ratio of manganese and N element are x: y: z: (1-x-y-z), 0 ＜ x ＜, 1,0 ＜ y ＜ 1,0 in formula ＜ z ＜ 1, x+y+z ＜ 1；Aqueous slkali and enveloping agent solution are prepared respectively；The doping metals N salt for containing metallic element N can Soluble compound, the N are any one or more in Zr, Mg, Al, Ti, Ce, Er element；(2) step (1) solution A, the mixing salt solution B, the aqueous slkali and the enveloping agent solution are individually pumped into In reaction kettle and it is stirred, mixing speed is 100~800rpm, controls the flow velocity of aqueous slkali and enveloping agent solution and makes mixing molten Liquid pH value is 9~13, and temperature of reaction kettle is controlled at 30~90 DEG C, and whole process is passed through inert gas shielding；Treat step (1) described mixing Salting liquid B continues to stir after all adding reaction kettle, and overflow to aging reactor is aged 5~36h, then passes through centrifuge filtering point From washing, 6~24h is finally dried at 80~200 DEG C, obtains nickel cobalt manganese hydroxide precursor；(3) step (2) the nickel cobalt manganese hydroxide precursor is mixed in proportion with lithium source, 6 is calcined at 700~1100 DEG C ~20h, crosses 200~400 mesh sieves after broken two pairs of rollers, obtains nickle cobalt lithium manganate C to be covered；(4) step (3) the nickle cobalt lithium manganate C is weighed in proportion with LiFePO4, is mixed, discharged by high-speed mixer 200~400 mesh sieves, obtain high security lithium ion positive electrode for battery material.
- A kind of 2. preparation method of high security lithium ion positive electrode for battery material as claimed in claim 1, it is characterised in that In the step (1), the alkaline concentration is 1~10mol/L.
- A kind of 3. preparation method of high security lithium ion positive electrode for battery material as claimed in claim 1, it is characterised in that In the step (1), the enveloping agent solution concentration is 1~10mol/L.
- A kind of 4. preparation method of high security lithium ion positive electrode for battery material as claimed in claim 1, it is characterised in that In the step (2), the nickel cobalt manganese hydroxide precursor pattern is long sheet.
- A kind of 5. preparation method of high security lithium ion positive electrode for battery material as claimed in claim 1, it is characterised in that In the step (3), the quality of the lithium source accounts for the 40~50% of nickel cobalt manganese hydroxide precursor gross mass.
- A kind of 6. preparation method of high security lithium ion positive electrode for battery material as claimed in claim 1, it is characterised in that In the step (3), the D50 of the nickle cobalt lithium manganate C to be covered is 3~20 μm, and pattern is single crystal grain.
- A kind of 7. preparation method of high security lithium ion positive electrode for battery material as claimed in claim 1, it is characterised in that In the step (4), the primary particle size of the LiFePO4 is 50~500nm.
- A kind of 8. preparation method of high security lithium ion positive electrode for battery material as claimed in claim 1, it is characterised in that In the step (4), the ratio that the LiFePO4 accounts for positive electrode is 1~30%.
- A kind of 9. preparation method of high security lithium ion positive electrode for battery material as claimed in claim 1, it is characterised in that In the step (4), the revolution of the high-speed mixer is 500~3000rpm, and incorporation time is 5~30min.
- A kind of 10. high security lithium ion positive electrode for battery material, using such as claim 1~9 any one the method system It is standby to obtain.
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