CN102569775B - Lithium-ion secondary battery and positive electrode active material thereof - Google Patents
Lithium-ion secondary battery and positive electrode active material thereof Download PDFInfo
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Abstract
The invention discloses a positive electrode active material of a lithium-ion secondary battery, which structurally comprises three layers, the three layers are respectively a matrix positioned on a center, a co-crystallizing grid layer covering the matrix and a covering layer covering the co-crystallizing grid layer, wherein the matrix is made from metallic oxide containing lithium, the co-crystallizing grid layer is made of the matrix material mixed with transition metal, and the material of the covering layer is metal oxide ZOi, phosphate Z (PO4)j or fluoride ZFk. Compared with prior art, the positive electrode active material of the lithium-ion secondary battery adopts a three-layer structural material in design, the covering layer on the outermost layer is made of stable ceramic material, the direct effect of electrolyte and active material can be effectively improved, the co-crystallizing grid layer and the matrix material are in eutectic cladding, so as to enable the transportation of Li+ to be free from blockage. Therefore, the purpose of expanding positive electrode active material charging to end voltage is achieved.
Description
Technical field
The present invention relates to lithium rechargeable battery, especially a kind of lithium rechargeable battery and its positive electrode active materials.
Background technology
In recent years, the development of the miniaturization of mobile electronic terminal, power vehicle battery and energy-storage battery is to lithium ion secondary
The energy density of battery proposes higher and higher requirement.People employ following various mode to improve lithium rechargeable battery
Energy density: the first, select the higher positive/negative active material of specific discharge capacity；Secondth, select voltage platform higher
Positive electrode active materials；3rd, reduce the mass ratio of inert matter and active material；4th, in the situation not changing negative pole
Under, directly improve the charge cutoff current potential of positive pole.4th kind of mode is to be also the most effectively a kind of mode, because
It can not only make the specific discharge capacity value of positive active material bigger, and the voltage platform enabling to battery is higher,
The first and second settling mode have been taken into account simultaneously.
But, the realization of the 4th kind of mode has very big technical barrier to need to capture.Usually, with layered cathode material it is
The charge cutoff voltage of the lithium rechargeable battery of active material is that (now positive pole is about 4.2v relatively with the current potential of li metal
4.25v).When the charge cutoff voltage of lithium rechargeable battery improves further, positive electrode active materials crystal structure can be by layer
Shape structure changes to spinel structure, and crystal structure can become very unstable so that the lithium ion of part abjection is ensuing
Cannot embedding in discharge process and return in positive electrode active materials, thus causing irreversible energy loss, leading to cycle life to subtract
Few；Furthermore, layer structure changes it is meant that the structure of material is reformed to spinel structure, plays skeletal support to structure
The oxygen atom of effect will migrate, and the easy oxidation electrolyte of the active oxygen atom in transition process makes lithium rechargeable battery
Internal temperature raise, cause danger.
In order to solve this problem, industry researcher is generally achieved the goal by material is modified with research.Example
As, United States Patent (USP) us7,381,497 prepare positive electrode active materials by the way of bulk phase-doped, can make the material to be higher than
Still there is during 4.25v more stable structure.But, this mode can not stop positive active material in high potential and electricity
Side reaction between solution liquid, therefore in long circulation with storing process, the active element of surface of positive electrode active material is (such as
Co) can be gradually dissolved in electrolyte, gradually decreasing with active element, the heat endurance of battery and cycle performance are deteriorated.
In addition, bulk phase-doped result means that other metallic atoms go to replace the active atomic of positive active material itself, this may
Change the electronic structure of material, or even change its specific discharge capacity.Obviously, this solution yet suffers from many problems does not have
Solve.United States Patent (USP) us6,783,890 and us7,807,298 then all using bulk phase-doped combine with Surface coating by the way of system
Standby positive electrode active materials.Although cladding can improve the surface stability of positive electrode active materials really, it is still unavoidable from
The negative effect that the bulk phase-doped material electronicses structure brought changes and causes, therefore there is also certain defect.
Chinese patent application cn101997113a disclose one kind prepared by multilayer (1～5 layer) cladding mode polynary
Material, wherein, clad and kernel are similar material all the time, and difference is only that the degree of ni element with clad
Increase be gradually reduced from inside to outside.Numerous scientific investigations showed that, the multicomponent material of this kind of high ni content, cycle performance is not excellent
Elegant the reason, is: the de- lithium that charges leads to ni ion to be changed into+4 valencys, ni from+divalent4+There is strong oxidizing property it is easy to and electrolyte
React, thus leading to the deterioration of battery performance.Obviously, the material of this disclosure of the invention has ni element to be exposed to material all the time
Surface, with electrolyte directly contact.Thus, improve the effect of material circulation performance by the method successively reducing ni constituent content
Fruit will be extremely limited.Furthermore, each interlayer of material that can be seen that this disclosure of the invention from Figure of description disclosed in it has more apparent
Space, the charge and discharge process leading to battery is become difficult by this, that is, lithium ion embed in the material and abjection during need
Cross over a plurality of " wide gap ", lead to power-performance not ideal enough.
In view of this, it is necessory to provide a kind of new lithium rechargeable battery and its positive electrode active materials.
Content of the invention
It is an object of the invention to: provide a kind of lithium rechargeable battery and its positive electrode active materials, to improve lithium ion
Efficiency first when secondary cell is applied in the case that charge cutoff voltage is higher than 4.1v, high-temperature storage performance, cycle performance
And security performance.
In order to realize foregoing invention purpose, the invention provides a kind of anode active material of lithium ion secondary battery, its knot
Structure is three layers, the matrix being in center respectively, the eutectic compartment being coated on matrix and the cladding being coated on eutectic compartment
Layer, matrix is containing lithium metal oxide, and eutectic compartment is matrix material through transient metal doped lithium metal oxide, clad
Material be metal oxide zoi, phosphate z (po4)jOr fluoride zfk；Z be li, al, ba, ca, cr, cu, mg, sn, sr,
One or more of ti, v, zr.
As anode active material of lithium ion secondary battery of the present invention one kind improvement, described matrix containing lithium metal oxidation
The general structure of thing is lixmoy, the general structure of eutectic compartment is lixm1-anaoy, wherein, m is in tri- kinds of elements of ni, co, mn
One or more, n is one or more of al, mg, zr, b, cr, ti, and 0.96≤x≤1.3,1.98≤y≤2.02,0
<a≤0.1.
As one kind improvement of anode active material of lithium ion secondary battery of the present invention, x, the a's in described general structure
Preferably span is respectively 0.96≤x≤1.2 and 0.002≤a≤0.06.
One kind improvement, described eutectic compartment material and matrix as anode active material of lithium ion secondary battery of the present invention
Material eutectic lattice, all containing ni element in two-layer, and degree in eutectic compartment for the ni element is less than ni element in base
Degree in body.
As one kind improvement of anode active material of lithium ion secondary battery of the present invention, described coating layer material is al2o3、
zro2、tio2、alpo4、li3po4、lif、mgo、alf3One or more of.
As one kind improvement of anode active material of lithium ion secondary battery of the present invention, the thickness of described eutectic compartment is 10
～200nm.
As one kind improvement of anode active material of lithium ion secondary battery of the present invention, the thickness lattice together of described matrix
The thickness of layer ratio is for 150:1～1000:1.
As one kind improvement of anode active material of lithium ion secondary battery of the present invention, the thickness of described clad is 50～
300nm.
One kind improvement, the thickness of described clad and matrix as anode active material of lithium ion secondary battery of the present invention
Thickness than for 50:1～500:1.
As one kind improvement of anode active material of lithium ion secondary battery of the present invention, the bet of described positive electrode active materials
For 0.1～10m2/ g, tap density is 1.5～3.0g/cm3.
In order to realize foregoing invention purpose, present invention also offers a kind of lithium rechargeable battery, it include anode pole piece,
Cathode pole piece, the barrier film being interval between anode pole piece and cathode pole piece, and nonaqueous electrolytic solution, wherein, anode pole piece by
Aforementioned positive electrode active material is coated on aluminium foil after uniformly being mixed with binding agent, conductive carbon powder and makes, the charge cutoff voltage of battery
Higher than 4.1v.
Compared with prior art, anode active material of lithium ion secondary battery of the present invention adopts three-layer structure material to design,
The clad on top layer is one layer of stable ceramic masses, can be effectively improved the direct effect of electrolyte and active material, and be total to
Lattice layer is coated with base matter eutectic, makes li+Transport unobstructed, thus be successfully realized expansion positive electrode active materials fill
The purpose of electric blanking voltage.
Brief description
With reference to the accompanying drawings and detailed description, the knot to lithium rechargeable battery of the present invention and its positive electrode active materials
Structure and Advantageous Effects are described in detail.
Fig. 1 is the structural representation of anode active material of lithium ion secondary battery of the present invention.
Fig. 2 is the embodiment of the present invention 1 and comparative example 1 efficiency first of the discharge and recharge under the charge cutoff voltage more than 4.1v
Comparison diagram.
Specific embodiment
Refer to shown in Fig. 1, anode active material of lithium ion secondary battery of the present invention includes three-decker, is in respectively
The matrix 10 at center, the eutectic compartment 20 being coated on matrix 10 and the clad 30 being coated on eutectic compartment 20.
Matrix 10 is containing lithium metal oxide, and its general structure can be expressed as lixmoy: wherein, m is tri- kinds of ni, co, mn
One or more of element, the span of x, y meets 0.96≤x≤1.3,1.98≤y≤2.02.The span of x is full
Foot 0.96≤x≤1.3 are because: during material sintering, li easily volatilizees because temperature is too high, so that causing a small amount of
Lithium disappearance；When li content brings up to x ＞ 1.3, li can be enriched with material surface, and then forms the impurity containing li, affects material
The high-temperature storage performance of material；But, in the excessive scope of li appropriateness, unnecessary li ion will go into the transition metal m (present invention
Refer in particular to ni, co and/or mn) lattice position that is located, the presence of this richness lithium structure will be helpful to improve the electrical conductivity of material and
Specific discharge capacity, therefore preferred 0.96≤x≤1.3.When y < when 1.98, the oxygen of transition disappearance by the m ion leading in material to
Lower valency changes, thus reducing the specific capacity containing lithium metal oxide；And as y > 2.02 when unnecessary oxygen atom can be caused to occupy
The transition metal lattice position of lithium metal oxide or be present in its interstitial void, the structural stability of impact material, because
This preferred 1.98≤y≤2.02.
For matrix material through transient metal doped lithium metal oxide, its general structure is li to eutectic compartment 20xm1- anaoy: wherein, m is one or more of tri- kinds of elements of ni, co, mn, and n is one of al, mg, zr, b, cr, ti or several
Kind, and 0.96≤x≤1.3,1.98≤y≤2.02,0 < a≤0.1, also require the material of eutectic compartment 20 and the material of matrix 10
Form lattice structure altogether.0 < a≤0.1 is because: n element is doped to be entered in the lattice of lithium metal oxide, and replaces this
Transition metal in body material, can reinforcing material structural stability, thus improve containing lithium metal oxide cyclical stability,
Even reduce the electric conductivity of material so that increasing its high rate performance, the present invention preferably 0.002≤a≤0.06.The span of x, y
Identical with the span of x, y in matrix 10.
The material of clad 30 is metal oxide (zoi), phosphate (z (po4)j) or fluoride (zfk), wherein, z is
One or more of li, al, ba, ca, cr, cu, mg, sn, sr, ti, v, zr.The cladding of clad 30 just would further weaken
Pole active material and the interaction of electrolyte, are conducive to improving the high-temperature behavior of battery and cyclical stability, and different
Inorganic salts are coated on and will show different superiority during the outermost layer of material, such as li3po4With lif due to its good lithium ion
Conductive capability, using them as the high rate performance that also can improve battery during outermost layer coating；For another example, use al2o3、zro2、
tio2During etc. good ceramic material as outermost layer coating, there is superior antiacid caustic corrosion performance, electricity can be substantially improved
The cycle performance in pond.Therefore, currently preferred outermost layer covering material is al2o3、zro2、tio2、mgo、li3po4、alpo4、
lif、alf3One or more of.
The THICKNESS CONTROL of application claims eutectic compartment 20 is in 10～200nm, the thickness of eutectic compartment 20 and matrix 10
Thickness is than for 150:1～1000:1.The THICKNESS CONTROL of clad 30 is in 50～300nm, the thickness of clad 30 and matrix 10
Thickness than for 50:1～500:1, this is because clad 30 is excessively thin will not have the effect of material modification protection, and clad 30
Blocked up the specific capacity due to the introducing of excessive inert matter, instead resulting in material is reduced.
It is 0.1～10m that the present invention also requires the specific surface area (bet) of positive electrode active materials2/ g, that is, through eutectic compartment 20 He
The bet of the positive electrode active materials after clad 30 cladding controls in 0.1～10m2/g.Because material activity point is generally become with bet
, that is to say, that the bet of material is bigger, the active site of material is also more for proportional relationship, the activity that material is acted on electrolyte
Higher, show is exactly that cycle performance, storage performance and security performance are poorer；When the bet of material is too small, material
Granularity will be bigger, its li+The passage of abjection/embedded is longer, will appear as that capacity is low, high rate performance is poor.Therefore, the present invention
In, the bet of positive electrode active materials is preferably 0.1～10m2/g.
The synthetic method of positive electrode active materials is: by the oxide (m of main metal element maob) and lithium carbonate (li2co3)
Ball mill is sufficiently mixed, then low-temperature sintering obtains predecessor a in air atmosphere；Predecessor a is evenly spread to use
In the nitrate solution of the metallic element n of surface doping, carry out liquid phase thermal response, in obtaining through filtration, washing taking precipitate
Mesosome b, wherein, n element is one or more of al, mg, zr, b, cr, ti of referring in the present invention；Again that b is dispersed
Nitrate, nah to z2po4Or/and in the solution of naf, through naoh, lioh or/and nh4It is adjusted to suitable ph in oh solution
Value, carry out liquid phase thermal response, through filter, washing taking precipitate obtain intermediate c, wherein, z be li according to the present invention, al,
One or more of ba, ca, cr, cu, mg, sn, sr, ti, v, zr.C material is dried, ball milling and high temperature sintering are designed
Material.Using icp, Atomic Absorption Spectrometer and chromatography of ions test out preparation containing lithium metal oxide (positive-active material
Material) in each element content, resulting materials outermost layer/intermediate layer/matrix is represented, such as al2o3/li1.02co0.98al0.02o2/
licoo2The material representing is licoo2Material is through li1.02co0.98al0.02o2After the eutectic lattice cladding of surface, then by al2o3It is coated on
The outermost layer of material.Finally, the bet of made positive electrode active materials is recorded using ratio surface area instrument.
The preparation method of lithium rechargeable battery:
Obtained positive electrode active materials, conductive carbon powder and pvdf are added sequentially to a certain amount of in the ratio of 90:5:5
Stir in n- methyl pyrrolidone, then slurry is equably coated on 14 μm of aluminium foil, just make through cut-parts, cutting
Pole pole piece is standby.
Negative pole adopts graphite, and barrier film is 16 μm of polypropylene porous isolating membrane, and electrolyte is 1m lipf6/ec+dec
(3:7), then anode pole piece, cathode pole piece, barrier film are assembled into battery, inject nonaqueous electrolytic solution, the lithium ion being assembled
The battery core capacity of negative plates of secondary cell is 1.10～1.20 than positive electrode capacity.
Embodiment 1: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
al2o3/li1.02co0.98al0.02o2.01/licoo2.Prepare according to above-mentioned preparation method and lithium metal oxide is contained as positive pole with this
Lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.27m2/ g, the test voltage scope of battery
For 3.0-4.6v.
Embodiment 2: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
tio2/li1.01co0.98al0.01o2.01/licoo2.Prepare according to above-mentioned preparation method and lithium metal oxide is contained as positive pole with this
Lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.18m2/ g, the test voltage scope of battery
For 3.0-4.6v.
Embodiment 3: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
zro2/li0.99co0.98al0.02o2.01/licoo2.Prepare according to above-mentioned preparation method and lithium metal oxide is contained as positive pole with this
Lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.22m2/ g, the test voltage scope of battery
For 3.0-4.6v.
Embodiment 4: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
li3po4/li1.0co0.98al0.01o2.01/licoo2.Prepare according to above-mentioned battery production method and with this containing lithium metal oxide be
The lithium ion battery of positive pole, recorded using ratio surface area instrument prepare material bet be 0.35m2/ g, the test voltage scope of battery
For 3.0-4.3v.
Embodiment 5: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
alpo3/li1.02co0.98al0.02o2.01/licoo2.Prepare according to above-mentioned preparation method and lithium metal oxide is contained as positive pole with this
Lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.74m2/ g, the test voltage scope of battery
For 3.0-4.2v.
Embodiment 6: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
alf3/li1.02co0.98al0.02o2.01/licoo2.Prepare according to above-mentioned preparation method and lithium metal oxide is contained as positive pole with this
Lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.75m2/ g, the test voltage scope of battery
For 3.0-4.6v.
Embodiment 7: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
alf3/li1.0co0.99mg0.01o2.02/licoo2.Prepare according to above-mentioned preparation method and lithium metal oxide is contained as positive pole with this
Lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.37m2/ g, the test voltage scope of battery is
3.0-4.4v.
Embodiment 8: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
lif/li0.99co0.98cr0.01o2.01/licoo2.Prepare according to above-mentioned preparation method and lithium metal oxide is contained as positive pole with this
Lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.44m2/ g, the test voltage scope of battery is
3.0-4.6v.
Embodiment 9: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
alf3/li1.02co0.995b0.005o1.98/licoo2.Prepare according to above-mentioned preparation method and lithium metal oxide is contained as positive pole with this
Lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 5.7m2/ g, the test voltage scope of battery
For 3.0-4.6v.
Embodiment 10: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
alf3/limn1/3ni1/3co0.31al0.02o2.01/limn1/3ni1/3co1/3o2.Prepare according to above-mentioned preparation method and lithium gold is contained with this
Belong to oxide be positive pole lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 7.2m2/ g, battery
Test voltage scope be 3.0-4.6v.
Embodiment 11: compound containing the lithium metal oxide material of 3-tier architecture be obtained according to above-mentioned material synthetic method:
lif/limn0.3ni0.5co0.19mg0.01o2.01/limn0.3ni0.5co0.19o2.Prepare according to above-mentioned preparation method and lithium gold is contained with this
Belong to oxide be positive pole lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 5.7m2/ g, battery
Test voltage scope be 3.0-4.6v.
Comparative example 1: licoo is obtained according to traditional preparation methods2.Prepare according to above-mentioned battery production method and contained with this
Lithium metal oxide be positive pole lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.42m2/ g,
The test voltage scope of battery is 3.0-4.6v.
Comparative example 2: li has conventionally been obtained1.01co0.98al0.02o2.01.According to above-mentioned battery production method system
For going out with this lithium rechargeable battery as positive pole containing lithium metal oxide, record the bet preparing material using ratio surface area instrument
For 0.15m2/ g, the test voltage scope of battery is 3.0-4.6v.
Comparative example 3: zro has conventionally been obtained2/licoo2.Prepare according to above-mentioned battery production method with this
Containing lithium metal oxide for positive pole lithium rechargeable battery, recorded using ratio surface area instrument prepare material bet be 0.27m2/
G, the test voltage scope of battery is 3.0-4.6v.
Comparative example 4: alf has been obtained according to the open method of document3//licoo2.According to above-mentioned battery production method preparation
Go out with this lithium rechargeable battery as positive pole containing lithium metal oxide, recorded using ratio surface area instrument and prepare the bet of material and be
0.38m2/ g, the test voltage scope of battery is 3.0-4.6v.
Comparative example 5: lif/li has been obtained according to the open method of document1.02co0.98al0.02o2.01.According to above-mentioned battery system
Prepare with this lithium rechargeable battery as positive pole containing lithium metal oxide as method, recorded using ratio surface area instrument and prepare material
The bet of material is 0.44m2/ g, the test voltage scope of battery is 3.0-4.6v.
Hereinafter the battery that embodiment and comparative example are obtained is tested, to detect various performances and the effect of the present invention
Really.
The charge cutoff voltage of the lithium rechargeable battery being assembled is more than 4.1v, first that lithium rechargeable battery is full
Charge to 4.6v, then lithium rechargeable battery be discharged to from 4.6v by 3.0v with the discharge-rate of 0.2c, this capacity be lithium from
Discharge capacity d of sub- secondary cell0, by discharge capacity d0Coating weight divided by positive electrode active materials obtains positive electrode active materials
The gram volume d of electric discharge firstspec.Then repeat above-mentioned charge step, be discharged to 3.0v under 1c and obtain lithium rechargeable battery
Discharge capacity d1, by d1Divided by d0Obtain the discharge-rate Capacity Ratio of lithium rechargeable battery 1c.
Prepared lithium rechargeable battery is placed under 60 degree and stores 30 days, the thickness change before and after record battery core storage
And capability retention.
Prepared lithium rechargeable battery is done at 45 DEG C the circulation between 1c/1c 3.0～charge cutoff voltage, follow
Ring records its capability retention after 300 weeks.
The test data table of table 1, embodiment and comparative example
| Embodiment | Voltage range | bet(m2/g) | 1c multiplying power | 60 degree of 30 days thickness changes | 300 circulation volume conservation rates |
| Embodiment 1 | 3.0-4.6v | 0.27 | 93% | 4% | 86% |
| Embodiment 2 | 3.0-4.6v | 0.18 | 90% | 14% | 84% |
| Embodiment 3 | 3.0-4.6v | 0.22 | 91% | 4% | 82% |
| Embodiment 4 | 3.0-4.3v | 0.35 | 94% | 3% | 90% |
| Embodiment 5 | 3.0-4.2v | 0.74 | 94% | 3% | 93% |
| Embodiment 6 | 3.0-4.6v | 0.75 | 94% | 9% | 86% |
| Embodiment 7 | 3.0-4.4v | 0.37 | 92% | 6% | 89% |
| Embodiment 8 | 3.0-4.6v | 0.44 | 95% | 13% | 87% |
| Embodiment 9 | 3.0-4.6v | 5.7 | 93% | 7% | 86% |
| Embodiment 10 | 3.0-4.6v | 7.2 | 96% | 14% | 82% |
| Embodiment 11 | 3.0-4.6v | 5.7 | 93% | 17% | 87% |
| Comparative example 1 | 3.0-4.6v | 0.42 | 95% | 121% | 56% |
| Comparative example 2 | 3.0-4.6v | 0.15 | 87% | 84% | 76% |
| Comparative example 3 | 3.0-4.6v | 0.27 | 91% | 52% | 67% |
| Comparative example 4 | 3.0-4.2v | 0.38 | 93% | 57% | 72% |
| Comparative example 5 | 3.0-4.6v | 0.44 | 95% | 21% | 81% |
Table 1 is the test data of embodiment 1-11 and comparative example 1-6 it can be seen that the improved three-decker of the present invention
Positive electrode active materials, its multiplying power under high voltages, storage performance and cycle performance, more existing raw material, simple adulterate
Material or/and simple covering material have different degrees of lifting.In addition, bet is also an important parameter, suitable bet will
Contribute to reducing the action intensity of material and electrolyte.
Refer to Fig. 2, be that the discharge and recharge under the charge cutoff voltage more than 4.1v of embodiment 1 and comparative example 1 is imitated first
Rate comparison diagram is it is seen then that the efficiency first of the embodiment of the present invention has clear improvement with respect to comparative example.
If ambiguously separately indicated, term used herein and phrase should be interpreted open and non-limiting
, such as the adjective of " conventional ", " traditional ", " known " etc is not necessarily to be construed as limiting described item with similar phrase
In given period, and should be read as understanding including any period of the present and the future or disclose conventional, traditional and known skill
Art；Term " eutectic lattice ", it is this area professional term, should be read as that " two or more has close or identical lattice
Condensed state matter grow together "；Term " lithium rechargeable battery " is this area professional term, should be read as " can entering
The lithium rechargeable battery of row cycle charging ".Term " bet ", be this area professional term, " specific surface area " should be read as.
Although it should be appreciated that having been incorporated with some specific embodiments to describe the present invention in detail, these enforcements
Example is merely to explain the present invention, rather than in order to limit the present invention.Although additionally, there is no exhaustive various combination kind in specification
Class, it will be appreciated by those skilled in the art that can be combined to various features according to the description of this specification, example
As the species of positive electrode is various, has just in the cobalt acid lithium of commercial applications, LiMn2O4, LiFePO 4, nickle cobalt lithium manganate
Deng also studying or will develop or knowable novel anode material, do not giving exhaustion in specification.
Claims (11)
1. a kind of anode active material of lithium ion secondary battery it is characterised in that: for three-decker, be in the base at center respectively
Body, the eutectic compartment being coated on matrix and the clad being coated on eutectic compartment, described matrix is containing lithium metal oxide,
For matrix material through transient metal doped lithium metal oxide, the material of clad is metal oxide zo to eutectic compartmenti, phosphorus
Hydrochlorate z (po4)jOr fluoride zfk；Z is one or more of li, al, ba, ca, cr, cu, mg, sn, sr, ti, v, zr.
2. anode active material of lithium ion secondary battery according to claim 1 it is characterised in that: described matrix containing lithium
The general structure of metal oxide is lixmoy, the general structure of eutectic compartment is lixm1-anaoy, wherein, m is ni, co, mn tri-
Plant one or more of element, n is one or more of al, mg, zr, b, cr, ti, and 0.96≤x≤1.3,1.98≤y
≤ 2.02,0 < a≤0.1.
3. anode active material of lithium ion secondary battery according to claim 2 it is characterised in that: in described general structure
X, a preferred span be respectively 0.96≤x≤1.2 and 0.002≤a≤0.06.
4. anode active material of lithium ion secondary battery according to claim 1 it is characterised in that: described eutectic compartment thing
Matter and base matter eutectic lattice, all containing ni element in two-layer, and degree in eutectic compartment for the ni element is less than ni
Element degree in the base.
5. anode active material of lithium ion secondary battery according to claim 1 it is characterised in that: described coating layer material
For al2o3、zro2、tio2、alpo4、li3po4、lif、mgo、alf3One or more of.
6. anode active material of lithium ion secondary battery according to claim 1 it is characterised in that: described eutectic compartment
Thickness is 10～200nm.
7. anode active material of lithium ion secondary battery according to claim 6 it is characterised in that: the thickness of described matrix
The thickness of lattice layer is than for 150:1～1000:1 together.
8. anode active material of lithium ion secondary battery according to claim 6 it is characterised in that: the thickness of described clad
Spend for 50～300nm.
9. anode active material of lithium ion secondary battery according to claim 6 it is characterised in that: the thickness of described clad
Degree and the thickness of matrix ratio is for 50:1～500:1.
10. anode active material of lithium ion secondary battery according to claim 1 it is characterised in that: described positive-active
The bet of material is 0.1～10m2/ g, tap density is 1.5～3.0g/cm3.
A kind of 11. lithium rechargeable batteries, including anode pole piece, cathode pole piece, are interval between anode pole piece and cathode pole piece
Barrier film, and nonaqueous electrolytic solution it is characterised in that: described anode pole piece is by any one of claim 1 to 10
Positive electrode active materials are coated on aluminium foil after uniformly being mixed with binding agent, conductive carbon powder and make, and the charge cutoff voltage of battery is higher than
4.1v.
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