CN109817968A - Surface-coated lithium nickel manganese oxide particles and method for producing same - Google Patents
Surface-coated lithium nickel manganese oxide particles and method for producing same Download PDFInfo
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Abstract
The present invention relates to surface-coated lithium nickel manganese oxide particles and a method for producing the same. The lithium nickel manganese oxide has a chemical formula of LiNi0.5Mn1.5O4At least part of the surface of the spinel type lithium nickel manganese oxide particles is coated with LiV1‑ xMxOPO4Wherein x is more than or equal to 0 and less than or equal to 0.9, and M is one or more doping metals selected from Y, Ca, Ce, K, Si, Mo, W, Mn, Fe, B, Mg, Al, Na, Zr and Ti. Because the surface of the lithium nickel manganese oxide is coated with the lithium vanadyl phosphate, the direct contact between the lithium nickel manganese oxide and the electrolyte can be prevented, and Mn is relieved3+Disproportionation and Mn4+The oxidation effect of the electrolyte can relieve the problem of battery core flatulence and improve the battery capacity and the first coulombic efficiency.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to through surface coated nickel ion doped particle and its manufacturer
Method.
Background technique
In recent years, with the rapid development of pure electric automobile and hybrid-electric car, develop high-energy, the long-life, it is low at
This electrochmical power source seems especially urgent, and lithium ion battery is high with its energy density, power density is high, operating voltage is high, puts certainly
The unique advantages such as electric rate is low, memory-less effect, has extended cycle life, is pollution-free are shown one's talent in field of chemical power source.In lithium ion
In cell positive material, spinel-type nickel ion doped (LiNi0.5Mn1.5O4) have that voltage platform is high, high rate performance is good, energy
Density height and it is at low cost the advantages that, it is considered to be most one of the anode material for lithium-ion batteries of future and attraction.With cobalt acid
Lithium is compared with nickel-cobalt-manganese ternary material, nickel ion doped high, at low cost, advantages of environment protection with voltage.Compared with LiMn2O4,
Nickel ion doped high temperature circulation stabilization is greatly improved.Compared with LiFePO4, nickel ion doped energy density is higher, batch of production
Secondary stability is good.Therefore, nickel ion doped is considered as the positive electrode of the following large-sized power battery first choice.
But because nickel ion doped material has high voltage platform, Mn when with electrolyte contacts, in nickel ion doped3+It can occur
Disproportionated reaction, and migrate to negative terminal surface and be catalyzed SEI film (solid electrolyte interface film, solid electrolyte
Interface regeneration), Mn4+Can oxidation electrolyte to cause electrolyte decomposition, the regeneration of SEI film and electrolyte
Decomposing finally can all cause battery core to produce gas expansion, influence the interface performance of electrode.
Summary of the invention
An aspect of of the present present invention provides a kind of through surface coated nickel ion doped particle, which is characterized in that the nickel mangaic acid
Lithium is that chemical formula is LiNi0.5Mn1.5O4Spinel-type nickel ion doped, the nickel ion doped particle at least part surface packet
Being covered with chemical formula is LiV1-xMxOPO4Vanadyl phosphate lithium, wherein 0≤x≤0.9, M be selected from Y, Ca, Ce, K, Si, Mo, W,
One or more doping metals of Mn, Fe, B, Mg, Al, Na, Zr, Ti.
Of the invention may be used as anode active material of lithium ion battery through surface coated nickel ion doped particle.Work as conduct
When battery anode active material, the nickel ion doped particle at least can be realized one of following effect:
Since nickel ion doped surface is coated by vanadyl phosphate lithium, can prevent or reduce nickel ion doped active material with
The Mn in nickel ion doped is alleviated in the direct contact of electrolyte3+Disproportionated reaction and Mn4+Oxidation, alleviate nickel ion doped battery core
Produce gas problem.
In addition, the vanadyl phosphate lithium due to cladding can also prevent Mn in nickel ion doped3+Disproportionated reaction, prevent cathode table
The regeneration of face SEI film, can effectively reduce the loss of active lithium in battery core.
On the other hand, because vanadyl phosphate lithium is there are lithium ion transport channel, the presence of vanadyl phosphate lithium clad accordingly subtracts
Lithium ion diffusion resistance in small solid phase, prevents the side reaction of nickel ion doped and electrolyte, can effectively increase positive electrode
Gram volume and coulombic efficiency for the first time.
Another aspect of the present invention provides method of the preparation through surface coated nickel ion doped particle, comprising the following steps:
(A) it provides comprising manganese source material, nickel source material, lithium source material, vanadium source material, phosphorus source material and optional doping gold
Belong to source material precursor mixture, wherein the doping metals be selected from Y, Ca, Ce, K, Si, Mo, W, Mn, Fe, B, Mg, Al,
Na, Zr, Ti's is one or more, and the dosage of the source material makes based on 1mol Ni, and the amount of Mn is 3~3.5mol, Li
Amount be 2~2.3mol, the amount of V is greater than 0~0.2mol, and the amount of P is greater than 0~0.2mol, the amount of doping metals is 0~
0.2mol；And
(B) under an oxygen-containing atmosphere or an inert atmosphere, the precursor mixture is roasted.
By means of the present invention, it can manufacture through surface coated nickel ion doped particle, and technique, equipment, control
It is at low cost, be conducive to large-scale production.
The another aspect of embodiment of the present invention provides a kind of positive active material, comprising described through surface coated nickel manganese
Sour lithium particle or as made from the method through surface coated nickel ion doped particle.
The another aspect of embodiment of the present invention provides a kind of lithium ion battery cell, which includes described
Through surface coated nickel ion doped particle or as made from the method through surface coated nickel ion doped particle.
The another aspect of embodiment of the present invention provides a kind of lithium ion battery, and the lithium ion battery includes described through table
The nickel ion doped particle or the manufacturing method that bread covers are obtained through surface coated nickel ion doped particle.
Positive active material of the invention, lithium ion battery cell, lithium ion battery, due to being wrapped containing described through surface
The nickel ion doped particle covered, can manufacture the battery of capacity and coulombic efficiency raising for the first time, and can effectively prevent and reduce
The flatulence problem of battery core.
Detailed description of the invention
The feature, advantage and technical effect of exemplary embodiment of the present described below with reference to the accompanying drawings.
Fig. 1 is the anode material for lithium-ion batteries LiNi of comparative example0.5Mn1.5O2SEM figure；
Fig. 2 is the anode material for lithium-ion batteries LiNi of embodiment 50.5Mn1.5O4/LiV0.92Na0.08OPO4SEM figure；
Fig. 3 is the experimental result that expansion rate test is carried out to battery core of the invention.
Specific embodiment
In order to be more clear goal of the invention of the invention, technical solution and advantageous effects, with reference to embodiments
The present invention will be described in further detail.It should be understood that embodiment described in this specification is just for the sake of explanation
The present invention, be not intended to limit the present invention, formula, ratio of embodiment etc. can adaptation to local conditions make a choice and reality had no to result
Matter influences.
For simplicity, some numberical ranges are only expressly disclosed herein.However, any lower limit can be with any upper limit group
Close the range for being formed and being not known and recording；And any lower limit can form the range for being not known and recording with other lower values, together
Any upper limit of sample can combine the range to be formed and not yet explicitly be recorded with any other upper limit.In addition, recorded although being not known,
Each point or single number between endpoints of ranges are included within the scope of this.Thus, each point or single number can be used as certainly
The lower limit or the upper limit of body, which combine with any other point or single number or combine to be formed with other lower limits or the upper limit, not yet explicitly to be recorded
Range.
Foregoing invention content of the invention is not intended to each disclosed embodiment or every kind of reality in the description present invention
Existing mode.Illustrative embodiments are more particularly exemplified described below.Many places in entire chapter application pass through a series of realities
It applies example and provides guidance, these embodiments can use in a variety of combinations.In various embodiments, described to enumerate only as generation
Table group should not be construed as exhaustion.
Through surface coated nickel ion doped particle
According to an aspect of the invention, there is provided a kind of through surface coated nickel ion doped particle, the nickel ion doped
Be chemical formula be LiNi0.5Mn1.5O4Spinel-type nickel ion doped, the nickel ion doped particle at least part surface cladding
Having chemical formula is LiV1-xMxOPO4Vanadyl phosphate lithium, wherein 0≤x≤0.9, M be selected from Y, Ca, Ce, K, Si, Mo, W, Mn,
One or more doping metals of Fe, B, Mg, Al, Na, Zr, Ti.
In through surface coated nickel ion doped particle, LiV1-xMxOPO4Mass content can be according to required electrode material
The performance of material determines, can select in 100ppm~50000ppm.
In addition, LiV in the particle1-xMxOPO4Content can pass through each element well known to well known ICP, ICP-MS etc.
The instrument of qualitative analysis and/or quantitative analysis is carried out to measure.
In addition, the D50 (median particle diameter) through surface coated nickel ion doped particle can be 0.1~20 μm.The D50 can
To measure and/or calculate by well known particle size determination device such as particle size analyzer.The partial size of nickel ion doped particle can basis
Performance, the technique of required electrode active material require appropriate selection.From raising performance of lithium ion battery, and mixing is not increased
From the point of view of the difficulty of dispersing technology, preferably 0.1~10 μm.
In one embodiment of the present of invention, the specific surface area through surface coated nickel ion doped particle can with 0.01~
20m2/g.Specific surface area can pass through the Instrument measuring of well known measurement the specific area.
For the LiV of nickel ion doped particle surface cladding1-xMxOPO4For, the value range of x is 0≤x≤0.9.
From the angle for improving electronic conductivity, lithium ion diffusion conductant rate, preferably 0.05≤x≤0.3.
The content ratio of various elements in the particle, such as relative to 1mol Ni, the content of Mn is 3~
The content of 3.04mol, Li are 2.64~3.32mol, and the content of V is 0.4~0.6mol, and the content of P is 0.4~0.6mol, is mixed
The content of miscellaneous metallic element M is 0~0.04mol.
Surface through surface coated nickel ion doped particle of the invention can partially be coated by the vanadyl phosphate lithium,
It can be wrapped by completely.In order to preferably reduce the Mn of nickel ion doped4+To the oxidation of electrolyte, prevent in nickel ion doped
Mn3+Disproportionated reaction, reduce battery core in active lithium loss from the aspect of, be preferably completely wrapped by.
Manufacturing method through surface coated nickel ion doped particle
According to an aspect of the present invention, a kind of manufacturing method through surface coated nickel ion doped particle is provided, including
Following steps:
(A) it provides comprising manganese source material, nickel source material, lithium source material, vanadium source material, phosphorus source material and optional doping gold
Belong to source material precursor mixture, wherein the doping metals be selected from Y, Ca, Ce, K, V, Si, Mo, W, Mn, Fe, B, Mg,
Al, Na, Zr, Ti's is one or more, and the dosage of the source material makes based on 1mol Ni, and the amount of Mn is 3~
The amount of 3.5mol, Li are 2~2.3mol, and the amount of V is 0~0.2mol, and the amount of P is 0~0.2mol, the amount of doping metals is 0~
0.2mol；And
(B) under an oxygen-containing atmosphere or an inert atmosphere, the precursor mixture is roasted.
The mixture proportionally mixed in advance can be used in a kind of embodiment according to the present invention, step (A),
Suitable each source material can also be used after mixing.
" manganese source material " described in this specification, " nickel source material ", " lithium source material ", " vanadium source material ", " phosphorus source material
Material " and " doping metals source material " are referred respectively to containing " manganese ", " nickel ", " lithium ", " vanadium ", " phosphorus " and " doping metals ", and are led to
Cross scheduled processing method, can be changed into " manganese element " in target product, " nickel element ", " elemental lithium ", " vanadium ",
" P elements " and " doped metallic elements ".It is preferred that other elements contained in source material, which are fired, is decomposed into gas and product point
From.
Above-mentioned material can choose well known commercially available product, can also be synthesized by well known method.
" the manganese source material " and " nickel source material " may select for spinelle LiNi0.5Mn1.5O4, also can choose
Other source materials containing manganese and nickel.Such as the oxide or hydroxide of manganese or nickel.In order to form spinelle LiNi0.5Mn1.5O4
The preferred 1:3 of the molar ratio of manganese or nickel element in the oxide or hydroxide of kernel, manganese or nickel.Such as it is preferable to use Ni0.5Mn1.5
(OH)4And Ni0.5Mn1.5O2One or both of, spinelle can be readily available using both nickel manganese source materials
LiNi0.5Mn1.5O4Kernel.
" lithium source material " can be salt, hydroxide containing lithium etc..Such as it can choose Li2CO3、LiOH·H2O、
LiNO3, one of LiCl or a variety of.
" vanadium source material " can be salt, oxide of vanadium containing vanadium etc..Such as it can choose VOPO4 2H2O、V2O5、
NH4VO3、VO(HPO4)0.5H2One of O or a variety of.
" phosphorus source material " can be phosphorous salt.Such as H3PO4、VO(HPO4)0.5H2O、VOPO4 2H2O、NH4H2PO4、
(NH4)2HPO4One of or it is a variety of, dopant metallic element M precursor can for the oxide of M, hydroxide, sulfate,
One or more of carbonate.
" doping metals source material " can be the substance containing the metal.Such as oxide, hydroxide, the sulphur of the metal
One or more of hydrochlorate, carbonate etc..Doping metals M can change the arrangement of d orbital electron, and it is embedding to reduce lithium ion abjection
Enter activation energy.In an embodiment of the invention, preferably Ti, Al, Mg, Na are selected Mg (OH) as doping metals2、
Na2CO3、Al2(CO3)3、Ti(OH)4Deng.
In one embodiment, material described in a section the Materials section can be used in the source material in step (A),
And each source material that will meet dosage described in step (A) mixes in a mixer in the presence of blending agent.
In the case where being mixed by mixer, blending agent for example can choose one kind or more of deionized water or alcohols
Kind, alcohols is one of ethyl alcohol, methanol, propyl alcohol, isopropanol or a variety of.Mixed revolving speed can be set according to mixture,
It can be 100~10000rpm, incorporation time can be 2~100h.
It, can be dry by well known drying means after mixing.In one embodiment of the invention, pass through spray drying
Equipment is dried, so that mixture becomes dry particle, treatment temperature can be 50~300 DEG C, revolving speed can for 1000~
30000rpm。
The dosage of the source material can be according to the content of the vanadyl phosphate lithium of the chemical formula and cladding of required product
It calculates.Preferably making Ni element relative to 1mol, the amount of Mn element is 3~3.04mol, the amount of Li element is 2.64~
3.32mol, the amount of V element are 0.4~0.6mol, and the amount of P element is 0.4~0.6, the amount of doped metallic elements M is 0~
0.04mol.Using the source material of the amount ranges, the nickel ion doped particle that can be evenly coated.
In addition, the roasting condition in step (B) can be carried out by usual method.For example, in one embodiment, heating
Speed is 1~10 DEG C/min, and sintering temperature is 400~1000 DEG C, and sintering time is 1~20h, and the gas that when roasting is passed through is sky
One of gas, oxygen, nitrogen, argon gas are a variety of.
In one embodiment, step (B) resulting product is directly ground up, sieved and obtains target product.In another reality
It applies in example, under an oxygen-containing atmosphere or an inert atmosphere, the product obtained to roasting makes annealing treatment, and the product after annealing is ground
Sieving obtains target product.By annealing, crystalline structure can be improved, keep unordered crystal form less, orderly crystal form is more.
Annealing can be carried out by well known method.In one embodiment, the cooling rate 1~10 of annealing
DEG C/min, sintering temperature is 500~700 DEG C, and sintering time is 1~15h.The gas being passed through when roasting can for air, oxygen,
One of nitrogen, argon gas are a variety of.
Positive active material
According to an aspect of the present invention, a kind of positive active material is provided, the positive active material includes described
Through surface coated nickel ion doped particle through surface coated nickel ion doped particle or as made from the manufacturing method.
The positive active material can be used for all batteries, especially lithium ion battery, and can effectively improve anode
Performance characteristic.
The example of " negative electrode active material " that is used cooperatively in the present invention with positive active material can be carbonaceous material such as
Crystallization or amorphous carbon or carbon composite (carbon, coke, the graphite of thermal decomposition), the organic polymer of burning, carbon fiber, oxygen
Change tin compound, lithium metal or lithium alloy.
Lithium ion battery cell
The lithium ion battery cell is made comprising described through surface coated nickel ion doped particle or by the method
Through surface coated nickel ion doped particle.
The manufacturing method of lithium ion battery cell is not particularly limited, and can pass through the method for the known in the art or following generation
To manufacture.In one embodiment, as a positive electrode active material by nickel ion doped particle of the present invention, with conventional conduction
After agent, binder are thoroughly mixed in dicyandiamide solution uniformly according to predetermined mass ratio, it is coated on plus plate current-collecting body, through drying
Anode pole piece can be obtained in dry, cold pressing.
By conventional negative electrode active material, conductive agent, binder, thickener etc. according to predetermined mass ratio in dicyandiamide solution
After being thoroughly mixed uniformly, it is coated on drying on negative current collector, cold pressing, obtains cathode pole piece.
Anode pole piece, isolation film, cathode pole piece are folded in order, isolation film is among positive and negative anodes and plays isolation
Effect, rolled available naked battery core.Naked battery core is placed in aluminum plastic film bag, the electrolyte prepared is injected and carries out hot pressing envelope
Dress, available battery core.
In addition, lithium ion battery cell of the present invention, due to using the surface coated nickel mangaic acid in the present invention
Lithium particle, therefore the Mn of nickel ion doped4+Mn in oxidation, and/or nickel ion doped to electrolyte3+Disproportionated reaction by
It prevents, therefore the loss of the active lithium in battery core use can be reduced, and produce gas problem after battery core storage can be improved.
According to the experiment of inventor, for battery core of the invention when storing number of days is 90 days, battery core expansion rate is below 30%.
It is further preferred that the expansion rate of battery core is below 25% when storage number of days is 90 days.
Lithium ion battery
According to an aspect of the present invention, a kind of lithium battery is provided, the lithium ion battery is wrapped comprising described through surface
The nickel ion doped particle covered or the manufacturing method are obtained through surface coated nickel ion doped particle.
In one embodiment, the lithium ion battery includes anode pole piece, cathode pole piece and electrolyte, wherein the present invention
Through surface coated nickel ion doped particle layer as a positive electrode active material, be set on collector.
The manufacturing method of lithium ion battery is not particularly limited, and known in this field or future usage method can be used.It can
Battery is assembled into instill battery core of the invention after appropriate electrolyte.
In one embodiment, as a positive electrode active material with nickel ion doped particle of the present invention, with predetermined weight and conduction
Agent, binder are sufficiently stirred in a solvent, after mixing, are coated on plus plate current-collecting body, then dry, and cold pressing obtains just
Pole pole piece.Anode pole piece is cut into after small pieces as anode, lithium piece is as cathode, and PP porous polymer film is as isolation film, drop
Battery is can be assembled into after entering appropriate electrolysis.
Lithium ion battery of the invention can be used as the power supply of any electric appliance or equipment, since spinel-type nickel ion doped has
Have the advantages that voltage platform is high, high rate performance is good, energy density is high and at low cost, is preferably used as the electricity of large-sized power vehicle
Pond.
In addition, the gram volume of battery and for the first time coulombic efficiency are higher than using uncoated according to the lithium ion battery
Battery made of nickel ion doped.According to the experiment of inventor, the coulombic efficiency for the first time of lithium ion battery of the invention be 88% with
On and/or gram volume be 130mAh/g or more.Preferably, the coulombic efficiency for the first time of lithium ion battery of the invention be 91% with
On and/or gram volume be 132mAh/g or more.
Embodiment
Following embodiments more particularly describe present disclosure, these being only intended to illustrate property of embodiment are said
It is bright, because carrying out various modifications and changing in scope of the present disclosure is obvious for a person skilled in the art
's.Unless otherwise stated, all parts, percentage and the ratio reported in following embodiment are by weight meter, Er Qieshi
It applies all commercially available industrial goods of all reagents used in example and can be used directly, unless otherwise stated, without further place
Reason.
Embodiment 1
Manufacture through surface coated nickel ion doped particle:
With Ni0.5Mn1.5(OH)4For nickel manganese presoma, with Li2CO3For lithium source, with VOPO4 2H2O is vanadium source and phosphorus source.It will
Above-mentioned precursor mixture is placed in mixer with molar ratio 1:0.83:0.3, and polyurethane ball and grinding medium are added in a mixer
Matter water, mixing revolving speed are 5000rpm, and incorporation time is for 24 hours.Above-mentioned mixed powder is carried out at nodularization by spray drying process
Reason, wherein spray drying temperature is 100 DEG C, and spraying revolving speed is 3000rpm.The powder after drying is then passed through into grinding appropriate
It is placed on progress high-temperature roasting processing in Muffle furnace, wherein high-temperature process temperature is 850 DEG C, and the processing time is 10h, heating rate
For 5 DEG C/min, the atmosphere being passed through is air, and it is 0.8L/min that gas, which is passed through speed,.It is coated after roasting by being ground up, sieved
There is the nickel ion doped material LiNi of vanadyl phosphate lithium0.5Mn1.5O4/LiVOPO4。
Embodiment 2
Manufacture through surface coated nickel ion doped particle:
With Ni0.5Mn1.5O2For nickel manganese precursor, with Li2CO3For lithium source, with V2O5For vanadium source, with NH4H2PO4For phosphorus source.It will
Above-mentioned powder is placed in mixer with molar ratio 1:0.72:0.1:0.2 and is uniformly mixed.Remaining experimentation and parameter and embodiment 1
It is identical, it is rear up to the anode material for lithium-ion batteries LiNi by being ground up, sieved0.5Mn1.5O4/LiVOPO4。
Embodiment 3
Manufacture through surface coated nickel ion doped particle:
Other than following conditions, preparation method is same as Example 1.With Ni0.5Mn1.5O2For nickel manganese precursor, LiOH
For lithium source, NH4VO3For vanadium source, NH4H2PO4For phosphorus source, Mg (OH)2And it adds doping and belongs to.By above-mentioned source material with molar ratio 1:
1.32:0.28:0.3:0.02 is placed in mixer, and polyurethane ball and abrasive media methanol are added in a mixer, mixes revolving speed
For 3000rpm, incorporation time 48h.Mixed powder is subjected to spray drying spheroidising, wherein spray drying temperature is 150
DEG C, spraying revolving speed is 5000rpm.By being ground up, sieved the nickel ion doped material for being coated with vanadyl phosphate lithium to obtain the final product after roasting
LiNi0.5Mn1.5O4/LiV0.93Mg0.07OPO4。
Embodiment 4
Manufacture through surface coated nickel ion doped particle:
Other than following conditions, preparation method is same as Example 3.Doping metals are Al2(CO3)3.By doing by spraying
The powder of dry spheroidising, high-temperature process temperature are 900 DEG C, and the processing time is 12h, and heating rate is 3 DEG C/min, the gas being passed through
Atmosphere is oxygen, and it is 1.0L/min that gas, which is passed through speed,.10h is roasted after being cooled to 650 DEG C after roasting with 3 DEG C/min.Lead to after roasting
It crosses and is ground up, sieved the nickel ion doped material LiNi for being coated with vanadyl phosphate lithium to obtain the final product0.5Mn1.5O4/LiV0.93Al0.07OPO4。
Embodiment 5
Manufacture through surface coated nickel ion doped particle:
Other than following conditions, preparation method is same as Example 3.With Ni0.5Mn1.5O2For nickel manganese precursor, LiNO3
For lithium source, V2O5For vanadium source, (NH4)2HPO4For phosphorus source, Na2CO3For doping metals.By above-mentioned source material with molar ratio 1:1.35:
0.13:0.2:0.01, which is placed in mixer, carries out mixed processing.6h is roasted after being cooled to 700 DEG C after roasting with 2 DEG C/min.Pass through
It is ground up, sieved the nickel ion doped material LiNi for being coated with vanadyl phosphate lithium to obtain the final product0.5Mn1.5O4/LiV0.92Na0.08OPO4。
Embodiment 6
Manufacture through surface coated nickel ion doped particle:
By nickel manganese precursor Ni0.5Mn1.5O2With lithium source Li2CO3It is placed in mixer and is mixed with molar ratio 1:0.51.Mixed
Polyurethane ball and abrasive media ethyl alcohol are added in clutch, mixing revolving speed is 5000rpm, and incorporation time is for 24 hours.It is logical after the completion of mixing
It crosses spray drying process and carries out spheroidising, wherein spray drying temperature is 150 DEG C, and spraying revolving speed is 5000rpm.It will then dry
Powder afterwards is placed on progress high-temperature roasting processing in Muffle furnace by grinding appropriate, and wherein high-temperature process temperature is 850 DEG C,
The processing time is 10h, and heating rate is 5 DEG C/min.The atmosphere being passed through is oxygen, and it is 0.8L/min that gas, which is passed through speed,.Roasting
Afterwards by being ground up, sieved up to uncoated nickel ion doped material LiNi0.5Mn1.5O4.Then by the LiNi of synthesis0.5Mn1.5O4With
Lithium source Li2CO3, vanadium source V2O5With phosphorus source NH4H2PO4It is placed in mixer and is uniformly mixed with molar ratio 1:0.012:0.01:0.02,
Wherein mixing revolving speed is 5000rpm, and incorporation time is for 24 hours.Mixed powder is then placed in progress high temperature roasting in Muffle furnace
Burning processing.High-temperature process temperature is 700 DEG C, and the processing time is 10h, and heating rate is 2 DEG C/min.The atmosphere being passed through is air,
It is 0.8L/min that gas, which is passed through speed,.By being ground up, sieved the nickel ion doped material for being coated with vanadyl phosphate lithium to obtain the final product after roasting
LiNi0.5Mn1.5O4/LiVOPO4。
Design parameter is as shown in table 1.
Table 1
Comparative example
By nickel manganese precursor Ni0.5Mn1.5O2With lithium source Li2CO3It is placed in mixer and is mixed with molar ratio 1:0.51.Mixed
Polyurethane ball and abrasive media ethyl alcohol are added in clutch, mixing revolving speed is 5000rpm, and incorporation time is that for 24 hours, mixing is logical after the completion
It crosses spray drying process and carries out spheroidising.Spray drying temperature is 100 DEG C, and spraying revolving speed is 3000rpm.It then will be after drying
Powder is placed on progress high-temperature roasting processing in Muffle furnace by grinding appropriate, and high-temperature roasting treatment temperature is 850 DEG C, processing
Time is 10h, and heating rate is 5 DEG C/min.The atmosphere being passed through is air, and it is 0.8L/min that gas, which is passed through speed,.Lead to after roasting
It crosses and is ground up, sieved up to uncoated nickel ion doped material LiNi0.5Mn1.5O4。
The design parameter of comparative example is as shown in table 2.
Table 2
Battery core Production Example
As a positive electrode active material by nickel ion doped particle made from embodiment 1,5,6 and comparative example, respectively with conductive agent
Acetylene black, binder polyvinylidene fluoride (PVDF) 95:2:3 in mass ratio are sufficiently stirred in N-Methyl pyrrolidone dicyandiamide solution
It mixes after mixing, is coated on drying on aluminium foil, cold pressing, obtains anode pole piece.
By negative electrode active material artificial graphite, conductive agent acetylene black, binder butadiene-styrene rubber, thickener carboxymethyl cellulose
After sodium is thoroughly mixed in deionized water solvent system uniformly according to mass ratio 90:5:2:2:1, coated on being dried on copper foil
Dry, cold pressing, obtains cathode pole piece.Using PE porous polymer film as isolation film.
Anode pole piece, isolation film, cathode pole piece are folded in order, isolation film is among anode and cathode and plays isolation
Effect, and wind and respectively obtain naked battery core 1,5,6 and comparison battery core.Naked battery core is placed in aluminum plastic film bag, the electricity prepared is injected
Solution liquid (such as high-voltage electrolyte) simultaneously carries out packaging by hot pressing, obtains battery core 1,5,6 and comparison battery core.
Battery manufacture example
Take the nickel ion doped particle as made from Examples 1 to 6 and comparative example as a positive electrode active material, respectively with conductive agent
Acetylene black, binder polyvinylidene fluoride (PVDF) are added in N-Methyl pyrrolidone solvent sufficiently by weight 92:4:4
It after being uniformly mixed, is coated on aluminium foil surface, then dries, cold pressing obtains anode pole piece.Anode pole piece is cut into small pieces
Afterwards as anode, lithium piece is assembled into battery after instilling appropriate electrolysis as isolation film as cathode, PP porous polymer film, point
It Biao Ji not be 1~6 and control cell.
Test result compares
(1) electron micrograph
Spinel nickel lithium manganate particle obtained in embodiment and comparative example is carried out by scanning electron microscope (SEM)
Shooting.
In comparative example untreated spinel nickel lithium manganate particle electron scanning micrograph as shown in Figure 1 (×
30000).It can be seen that, uncoated nickel ion doped particle is in regular crystal structure from SEM electron microscopic picture.
The electron scanning micrograph of the nickel ion doped being coated that embodiment 5 is prepared as shown in Figure 2 (×
30000).It can be seen that after vanadyl phosphate lithium cladding from SEM electron microscopic picture, one layer of cladding substance, material table occurs in surface
Face is not destroyed.
(2) storage produces gas comparative experiments
Under the same conditions to be prepared in " battery core Production Example " battery core 1,5,6 and comparison battery core carry out storage produce gas pair
Than experiment.
After battery core 1,5,6 and comparison battery core are carried out chemical conversion treatment, full battery is expired and is filled, is placed in 60 DEG C of insulating boxs, often
It tests its volume within 15 days, carries out storage and produce gas comparative experiments.
The volume initially measured is calculated as V0, the volume measured is calculated as V within the 15th day15, the volume measured is calculated as V within the 30th day30, the
45 days volumes measured are V45, and so on, the volume measured is calculated as V within n-th dayn。
Battery core expansion rate is calculated according to such as following formula (1):
Battery core expansion rate (%)=(Vn-V0)/V0× 100% formula (1)
The expansion rate measured is depicted as curve graph, obtains experimental result shown in Fig. 3.
From the figure 3, it may be seen that battery core 1,5,6 and the expansion rate difference for comparing battery core are smaller when storing number of days is 15 days, with
Storage time is elongated, and battery core 1,5,6 and the expansion rate difference for comparing battery core increase.When store number of days be 90 days when, by battery core 1,
5,6 and compare battery core expansion rate be 30% hereinafter, battery core 1,5 expansion rates 25% hereinafter, and by the expansion rate of comparison battery core
More than 35%.
It can be seen that through Gao Wencun after the anode material for lithium-ion batteries assembled battery being prepared using condition of the present invention
Chu Hou, battery core expansion rate are significantly reduced relative to comparative example.
In addition, cubical expansivity of the battery core 6 when storing 60 days and storing 90 days is higher than battery core 1,5, thus it is speculated that reason is such as
Under.Particle obtained by embodiment 6 has been used in battery core 6, and is with nickel ion doped (LiNi in embodiment 60.5Mn1.5O4) it is nickel
Manganese source material, the nickel manganese since nickel ion doped has formed particle, when with vanadyl phosphate lithium source material calcination, as kernel
Sour lithium particle is larger, and vanadyl phosphate lithium is difficult to be evenly coated.
(3) gram volume and for the first time coulombic efficiency (head effect) comparative experiments
Using blue electric electrochemical workstation, according to test gram volume and the standard method of coulombic efficiency for the first time, to " battery system
Make example " in battery 1~6 obtained tested with control cell, button electrical testing multiplying power is 0.1C, discharge voltage is 3.0~
4.95V。
Obtained experimental result is as shown in table 3.
Table 3
| Project | Unit | Battery 1 | Battery 2 | Battery 3 | Battery 4 | Battery 5 | Battery 6 | Control cell |
| Gram volume | mAh/g | 133.4 | 132.9 | 132.7 | 134.4 | 135.7 | 131.3 | 125.5 |
| Head effect | % | 92 | 91 | 92 | 93 | 93 | 88 | 86 |
Table 3 is it is found that the gram volume of battery 1~6 is imitated in 131 or more, head 88% or more, higher than the 125.5 of comparative example
With 86%.The gram volume of battery 1~5 is in 132 or more, head effect 91% or more.That is, the capacitance of battery 1~6 and for the first time
Efficiency is significantly improved relative to control cell.
From " battery manufacture example " part it is found that battery 1~6 and control cell have used Examples 1 to 6 and right respectively
Particle obtained in ratio.Can speculate in conjunction with the experimental result of table 3: by vanadyl phosphate lithium cladding after, electrolyte with contain
The contact area of the positive electrode of nickel ion doped particle reduces, and positive interface side reaction is reduced, and the performance of battery is improved.
In addition, the gram volume of battery 6 and first effect are below using the substance except nickel ion doped as the reality of nickel manganese source material
Apply example 1~4.Due to the particle that battery 6 has used embodiment 6 to manufacture, and nickel ion doped is used in embodiment
(LiNi0.5Mn1.5O4) it is used as nickel manganese source material.Therefore speculate that the reason of 6 performance of battery is lower than Examples 1 to 4 is using nickel manganese
Sour lithium (LiNi0.5Mn1.5O4) be used as nickel manganese source material when, the nickel ion doped particle as kernel is big, and vanadyl phosphate lithium is difficult to wrap
It covers uniformly.As use such as Ni0.5Mn1.5(OH)4、Ni0.5Mn1.5O2Etc nickel manganese source material when, nickel ion doped
(LiNi0.5Mn1.5O4) generation and the cladding of vanadyl phosphate lithium carry out simultaneously, nickel ion doped (LiNi0.5Mn1.5O4) kernel is smaller,
Cladding is more evenly.
In addition, the gram volume of battery 4,5 and first effect are better than battery 1~3.Since battery 4,5 and battery 1~3 make respectively
The particle made from embodiment 4,5 and 1~3, therefore speculate that the reason of battery 4,5 is better than battery 1~3 is in Examples 1 to 3
Without annealing after roasting source material, and it have passed through annealing in embodiment 4,5.
Although by reference to preferred embodiment, invention has been described, the case where not departing from the scope of the present invention
Under, various improvement can be carried out to it and can replace component therein with equivalent.Especially, as long as there is no structures to rush
Prominent, items technical characteristic mentioned in the various embodiments can be combined in any way.The invention is not limited to texts
Disclosed in specific embodiment, but include all technical solutions falling within the scope of the claims.
Claims (16)
1. a kind of through surface coated nickel ion doped particle, which is characterized in that the nickel ion doped is that chemical formula is
LiNi0.5Mn1.5O4Spinel-type nickel ion doped, at least part surface of the nickel ion doped particle is coated with chemical formula and is
LiV1-xMxOPO4Vanadyl phosphate lithium, wherein 0≤x≤0.9, M be selected from Y, Ca, Ce, K, Si, Mo, W, Mn, Fe, B, Mg, Al,
One or more doping metals of Na, Zr, Ti.
2. according to claim 1 through surface coated nickel ion doped particle, which is characterized in that coated described through surface
Nickel ion doped particle in, LiV1-xMxOPO4Mass content be 100ppm~50000ppm.
3. according to claim 1 through surface coated nickel ion doped particle, which is characterized in that described through surface coated
The D50 of nickel ion doped particle is 0.1~20 μm and/or specific surface area is 0.01~20m2/g。
4. according to claim 1 through surface coated nickel ion doped particle, which is characterized in that 0.05≤x≤0.3.
5. it is according to claim 1 through surface make reprisals nickel ion doped particle, which is characterized in that M be selected from Ti, Al, Mg,
One or more doping metals of Na.
6. according to claim 1 through surface coated nickel ion doped particle, which is characterized in that
In the particle, relative to 1mol Ni, the content of Mn is 3~3.04mol, and the content of Li is 2.64~3.32mol, V
Content be 0.4~0.6mol, the content of P is 0.4~0.6mol, and the content of doped metallic elements M is 0~0.04mol.
7. through surface coated nickel ion doped particle described according to claim 1~any one of 6, which is characterized in that institute
The surface for stating nickel ion doped particle is coated completely by the vanadyl phosphate lithium.
8. a kind of prepare the method described in claim 1 through surface coated nickel ion doped particle, which is characterized in that including with
Lower step:
(A) provide includes manganese source material, nickel source material, lithium source material, vanadium source material, phosphorus source material and optional doping metals source
The precursor mixture of material, wherein the doping metals be selected from Y, Ca, Ce, K, Si, Mo, W, Mn, Fe, B, Mg, Al, Na,
Zr, Ti's is one or more, and the dosage of the source material makes based on 1mol Ni, and the amount of Mn is 3~3.5mol, Li's
Amount is 2~2.3mol, and the amount of V is greater than 0~0.2mol, and the amount of P is greater than 0~0.2mol, the amount of doping metals is 0~
0.2mol；And
(B) under an oxygen-containing atmosphere or an inert atmosphere, the precursor mixture is roasted.
9. according to the method described in claim 8, it is characterized by further comprising:
Under an oxygen-containing atmosphere or an inert atmosphere, the product obtained to roasting makes annealing treatment.
10. according to the method described in claim 8, it is characterized in that,
The manganese source material and nickel source material is Ni0.5Mn1.5(OH)4And Ni0.5Mn1.5O2One or both of.
11. according to the method described in claim 8, it is characterized in that,
Lithium source material is Li2CO3、LiOH·H2O、LiNO3, one of LiCl or a variety of, vanadium source material is VOPO4 2H2O、
V2O5、NH4VO3、VO(HPO4)0.5H2One of O or a variety of, phosphorus source material are H3PO4、VO(HPO4)0.5H2O、VOPO4 2H2O、
NH4H2PO4、(NH4)2HPO4One of or it is a variety of, dopant metallic element M precursor be M oxide, hydroxide, sulphur
One or more of hydrochlorate, carbonate.
12. according to the method for claim 11, which is characterized in that
The dosage of the source material makes relative to 1mol Ni, and the amount of Mn is 3~3.04mol, and the amount of Li is 2.64~
The amount of 3.32mol, V are 0.4~0.6mol, and 0.4~0.6mol of amount: the amount of doped metallic elements M of P is 0~0.04mol.
13. a kind of positive active material, which is characterized in that comprising described in claim 1~7 through surface coated nickel ion doped
Through surface coated nickel ion doped particle made from particle or the method as described in any one of claim 8 to 12.
14. a kind of lithium ion battery cell, which is characterized in that the lithium ion battery cell includes any in claim 1 to 7
Through being passed through made from surface coated nickel ion doped particle or the method as described in any one of claim 8 to 12 described in item
Surface coated nickel ion doped particle.
15. lithium ion battery cell according to claim 14, which is characterized in that the lithium ion battery cell is storing
When number of days is 90 days, battery core expansion rate is 30% or less.
16. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes described in any one of claims 1 to 7
Through made from method described in any one of surface coated nickel ion doped particle or claim 8 to 12 through surface coated
Nickel ion doped particle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111180702A (en) * | 2020-01-06 | 2020-05-19 | 天能帅福得能源股份有限公司 | Preparation method of coated lithium manganate positive electrode material and positive electrode material thereof |
| WO2023115527A1 (en) * | 2021-12-24 | 2023-06-29 | 宁德时代新能源科技股份有限公司 | Spinel-type nickel-manganese-lithium-containing composite oxide, preparation method therefor, and secondary battery and electric device comprising same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050003274A1 (en) * | 1996-04-23 | 2005-01-06 | Michel Armand | Cathode materials for secondary (rechargeable) lithium batteries |
| CN101807691A (en) * | 2010-04-19 | 2010-08-18 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing lithium position sodium-doped oxygen lithium vanadium phosphate anode material of lithium ion battery |
| CN101841027A (en) * | 2010-05-13 | 2010-09-22 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing lithium position rare earth-doped lithium vanadyl phosphate cathode material for lithium ion battery |
| CN102299310A (en) * | 2011-07-13 | 2011-12-28 | 奇瑞汽车股份有限公司 | Preparation method for LiNi0.5Mn1.5O4 material and lithium ion battery prepared by materials |
| CN102709551A (en) * | 2012-05-22 | 2012-10-03 | 吉首大学 | Preparation method of manganese-doped lithium vanadyl phosphate anode material for lithium ion battery |
| CN102709552A (en) * | 2012-05-22 | 2012-10-03 | 吉首大学 | Preparation method of iron-doped lithium vanadium oxygen phosphate (LiVOPO4) positive material for lithium ion battery |
| CN104037409A (en) * | 2013-03-05 | 2014-09-10 | 吉首大学 | Preparation method for titanium-doped lithium vanadyl phosphate positive electrode material used for lithium ion battery |
| CN106784726A (en) * | 2017-01-18 | 2017-05-31 | 长安大学 | Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof |
-
2017
- 2017-11-21 CN CN201711167448.2A patent/CN109817968B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050003274A1 (en) * | 1996-04-23 | 2005-01-06 | Michel Armand | Cathode materials for secondary (rechargeable) lithium batteries |
| CN101807691A (en) * | 2010-04-19 | 2010-08-18 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing lithium position sodium-doped oxygen lithium vanadium phosphate anode material of lithium ion battery |
| CN101841027A (en) * | 2010-05-13 | 2010-09-22 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing lithium position rare earth-doped lithium vanadyl phosphate cathode material for lithium ion battery |
| CN102299310A (en) * | 2011-07-13 | 2011-12-28 | 奇瑞汽车股份有限公司 | Preparation method for LiNi0.5Mn1.5O4 material and lithium ion battery prepared by materials |
| CN102709551A (en) * | 2012-05-22 | 2012-10-03 | 吉首大学 | Preparation method of manganese-doped lithium vanadyl phosphate anode material for lithium ion battery |
| CN102709552A (en) * | 2012-05-22 | 2012-10-03 | 吉首大学 | Preparation method of iron-doped lithium vanadium oxygen phosphate (LiVOPO4) positive material for lithium ion battery |
| CN104037409A (en) * | 2013-03-05 | 2014-09-10 | 吉首大学 | Preparation method for titanium-doped lithium vanadyl phosphate positive electrode material used for lithium ion battery |
| CN106784726A (en) * | 2017-01-18 | 2017-05-31 | 长安大学 | Vanadyl phosphate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111180702A (en) * | 2020-01-06 | 2020-05-19 | 天能帅福得能源股份有限公司 | Preparation method of coated lithium manganate positive electrode material and positive electrode material thereof |
| WO2023115527A1 (en) * | 2021-12-24 | 2023-06-29 | 宁德时代新能源科技股份有限公司 | Spinel-type nickel-manganese-lithium-containing composite oxide, preparation method therefor, and secondary battery and electric device comprising same |
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