CN102237518A - Treatment method for ternary material and method for improving capacity and cycle performance of lithium battery - Google Patents
Treatment method for ternary material and method for improving capacity and cycle performance of lithium battery Download PDFInfo
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- CN102237518A CN102237518A CN2010101706381A CN201010170638A CN102237518A CN 102237518 A CN102237518 A CN 102237518A CN 2010101706381 A CN2010101706381 A CN 2010101706381A CN 201010170638 A CN201010170638 A CN 201010170638A CN 102237518 A CN102237518 A CN 102237518A
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- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 title description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 229910013716 LiNi Inorganic materials 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 229910012820 LiCoO Inorganic materials 0.000 claims description 15
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 238000003672 processing method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 3
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 abstract 4
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 12
- 229910012516 LiNi0.4Co0.2Mn0.4O2 Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229910012742 LiNi0.5Co0.3Mn0.2O2 Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 230000004087 circulation Effects 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 230000002459 sustained effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910004493 Li(Ni1/3Co1/3Mn1/3)O2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a treatment method for a ternary material LiNixCoyMnzO2(x+y+z). The method comprises the following steps of: firstly, adjusting the pH value of a LiNixCoyMnzO2 material to be alkaline or strongly alkaline and range from 8.0 to 12.0; secondly, gradually adding a cobalt salt solution into the alkaline or strongly alkaline LiNixCoyMnzO2 turbid liquid; and finally, drying the mixed material, adding a proper amount of lithium salt, and firing the mixture for 5 to 24 hours at a proper temperature in an air atmosphere to prepare the LiNixCoyMnzO2 material with a LiCoO2 treated surface. The method is simple in process; and the prepared product has high electrochemical performance within a high voltage range and is favorable for large-scale production.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of ternary material processing method, the ternary material that this disposal methods obtains, and to promote with the ternary material be the method for the capacity of lithium ion battery and the cycle performance of positive electrode, described ternary material is LiNi
xCo
yMn
zO
2, x+y+z=1.
Background technology
Lithium rechargeable battery have have extended cycle life, plurality of advantages such as the big and memory-less effect of discharging voltage balance, specific capacity, make it more and more be subjected to the public's concern and favor in the extensive use of numerous areas such as mobile phone, notebook computer and portable electronic device.
Calendar year 2001, Japanese scientist T.Ohzuku seminar adopts high temperature solid-state method to synthesize Li (Ni
1/3Co
1/3Mn
1/3) O
2Positive electrode, and reported with its chemical property as anode material for lithium-ion batteries (Ohzuku, T.; Makimura, Y.Chem.Lett.2001,642.).Studies show that this material has and stratiform LiNiO
2And LiCoO
2Similar structure belongs to hexagonal crystal system, is α-NaFeO
2The type layer structure.Because stratiform Li (Ni
1/3Co
1/3Mn
1/3) O
2Theoretical capacity is 278mAh/g, is being that voltage range is under the 3.0-4.2V condition in the full battery to electrode with graphite, and the discharge gram volume of the actual performance of ternary material is about 160-170mAh/g, far above the LiCoO of industrialization
2(145-150mAh/g) have excellent heavy-current discharge and cyclical stability, and Heat stability is good when overcharging, be a kind of high performance lithium ion battery anode material, thereby caused people's common concern, and realized industrialization soon.
In recent years, along with the fast development of information industry, the particularly continuous growth of China 3G business, obviously, volume energy density, the mass energy density of lithium ion battery all are difficult to satisfy the demand of people to high-capacity battery at present.High voltage helps promoting the performance of material discharging gram volume, as the method for a kind of effective lifting volume energy density and mass energy density, is adopted (by promoting with LiCoO by more external first-class battery manufacturers
2For the voltage range of the lithium ion battery of positive electrode promotes the battery specific capacity).Ternary material LiNi
xCo
yMn
zO
2(x+y+z=1) with its lower price, high multiplying power discharging property, excellent cycle performance has obtained people's common concern.When voltage range when 3.0-4.2V is increased to 3.0-4.3V, ternary material LiNi
xCo
yMn
zO
2(x+y+z=1) discharge gram volume performance can be promoted to 171-182mAh/g from about original 160-170mAh/g.Yet, under high voltage, LiNi
xCo
yMn
zO
2Material is easy to react with electrolyte, produces a large amount of gas and causes relatively poor cyclical stability and security performance.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of simple ternary material processing method is provided, this procedure is simple, and product has good electrochemical, is convenient to large-scale production.
Another object of the present invention is to provide a kind of ternary material that obtains by above-mentioned disposal methods.
It is the method for the capacity of lithium ion battery and the cycle performance of positive electrode with the ternary material that a further object of the present invention is to provide a kind of lifting.
For achieving the above object, the present invention has adopted following technical scheme:
The invention discloses a kind of ternary material processing method, described ternary material is LiNi
xCo
yMn
zO
2, x+y+z=1, described method comprises,
A, the ternary material powder added add alkaline solution behind the water furnishing pulpous state and regulate the pH value to 8.0-12.0;
B, in the product of steps A, add the solubility cobalt salt solution and fully react;
Add lithium salts after C, the product oven dry, in 500-1000 ℃ of abundant calcination with step B;
The addition of step B cobalt salt and step C lithium salts is according to the LiCoO that generates
2Account for LiCoO
2Add with the ratio of ternary material gross mass 1%～10%.
Preferably, the addition of step B cobalt salt and step C lithium salts is according to the LiCoO that generates
2Account for LiCoO
2Add with the ratio of ternary material gross mass 3%～7%.
In the steps A, described alkaline solution is preferably ammoniacal liquor or the LiOH solution of concentration 1-10mol/L; The preferred pH value of regulating is to 10.0-12.0.
Among the step B, described solubility cobalt salt is preferably at least a in acetic acid cobalt salt, citric acid cobalt salt or the nitric acid cobalt salt.Concentration is preferably 1～10mol/L.Described abundant reaction is meant was constantly fully reacting 1-5 hour under the condition of stirring.
Among the step C, described lithium salts is preferably Li
2CO
3, Li
2At least a among O or the LiOH.Described oven dry is preferable under 100～150 ℃ to be carried out, the preferred calcination 5-24 of described abundant calcination hour.
The invention also discloses by said method and handle the ternary material that obtains.
The present invention further discloses the method that a kind of lifting is the capacity of lithium ion battery and the cycle performance of positive electrode with the ternary material, comprise with said method ternary material is handled, described ternary material is LiNi
xCo
yMn
zO
2, x+y+z=1.
Owing to adopted above technical scheme, the beneficial effect that the present invention is possessed is:
Obtain ternary material through method processing of the present invention, the untreated ternary material of comparing, when being used to make lithium ion battery, can promote battery capacity and cycle performance, under high voltage, have good electrochemical especially as anode material for lithium-ion batteries.Procedure of the present invention is simple, is convenient to large-scale production.
Description of drawings
Fig. 1 is LiCoO prepared among the embodiment 1
2The LiNi that handles
0.4Co
0.2Mn
0.4O
2The XRD spectra of ternary powder body material.
Fig. 2 is LiCoO prepared among the embodiment 2
2The LiNi that handles
0.4Co
0.2Mn
0.4O
2The XRD spectra of ternary powder body material.
Fig. 3 is LiCoO prepared among the embodiment 3
2The LiNi that handles
0.5Co
0.3Mn
0.2O
2The XRD spectra of ternary powder body material.
Fig. 4 is LiCoO prepared among the embodiment 4
2The LiNi that handles
0.5Co
0.3Mn
0.2O
2The XRD spectra of ternary powder body material.
Fig. 5 is LiNi
0.4Co
0.2Mn
0.4O
2And LiNi
0.5Co
0.3Mn
0.2O
2Material is at the cyclic curve of 3.0-4.3V.
Fig. 6 is LiNi
0.4Co
0.2Mn
0.4O
2, the LiCoO of embodiment 1 and embodiment 2 preparations
2Surface-treated LiNi
0.4Co
0.2Mn
0.4O
2Material is at the cyclic curve of 3.0-4.3V.
Fig. 7 is LiNi
0.5Co
0.3Mn
0.2O
2, the LiCoO of embodiment 3 and embodiment 4 preparations
2Surface-treated LiNi
0.5Co
0.3Mn
0.2O
2Material is at the cyclic curve of 3.0-4.3V.
Embodiment
The present invention relates to a kind of simple ternary material LiNi
xCo
yMn
zO
2(x+y+z=1) surface treatment method.
Method of the present invention mainly comprises
(1) ternary material LiNi
xCo
yMn
zO
2(x+y+z=1) pre-treatment:
With LiNi
xCo
yMn
zO
2(x+y+z=1) an amount of water of powder body material adding is adjusted to the mud pulpous state.Dispose ammoniacal liquor or the LiOH solution of the preferred 1-10mol/L of an amount of concentration then, under continuous condition of stirring with LiNi
xCo
yMn
zO
2(x+y+z=1) the pH value of suspension-turbid liquid is adjusted to 8.0-12.0 (alkalescence, strong basicity).The size of alkalescence influences the speed of subsequent reactions, and alkalescence is strong more, and subsequent reactions speed is fast more, so preferably regulate the pH value to 10.0-12.0.
(2) preparation of finish materials:
The cobalt salt solution of the preferred 1-10mol/L of configuration debita spissitudo under continuous stirring condition, progressively adds cobalt salt solution the LiNi of the above-mentioned pH of regulating value
xCo
yMn
zO
2(x+y+z=1) suspension-turbid liquid.And in room temperature, constantly fully reaction under the condition of stirring preferred reaction 1-5 hour, is preferably dried in 100-150 ℃ baking oven afterwards.
Adding cobalt salt is in order to introduce cobalt element, therefore so long as can be in the afterglow process of back other elements except that cobalt can burn all solubility cobalt salts of removal all applicable to the present invention, such as, can select at least a in acetic acid cobalt salt, citric acid cobalt salt or the nitric acid cobalt salt for use.
(3) preparation of final material:
The material of oven dry is added an amount of lithium salts, fully mix the back in air atmosphere, the suitably abundant calcination of calcination temperature, reaction is down finished to be preferable over 500-1000 ℃ of calcination 5-24 hour, obtains end product.
Add lithium salts and be in order to introduce elemental lithium, therefore so long as can be in the afterglow process of back other elements except that lithium can burn all lithium salts of removal equally all applicable to the present invention, such as, preferred Li
2CO
3, Li
2At least a among O or the LiOH.
Above-mentioned steps (2) and (3) make in the afterglow process of back in ternary material surface generation cobalt acid lithium LiCoO by introducing cobalt element and elemental lithium
2In the method for the invention, should guarantee that the quality that generates cobalt acid lithium accounts for LiCoO
2With 1%～10% of ternary material gross mass, preferred 3%～7%, so the cobalt salt and the lithium salts that are added in above-mentioned steps (2) and (3), also should add with reference to this consumption principle substantially.
Wherein, lithium salts can be suitably excessive with respect to cobalt salt, such as, the mol ratio of Li, Co at 1-1.05: all can in 1 scope.Especially, when in step (1), utilizing LiOH to regulate the pH value, owing to introduced the part elemental lithium, so the lithium salts that is added in the step (3) can suitably reduce, and only need make the total amount of Li element and the mol ratio of Co element satisfy above-mentioned 1-1.05 substantially: 1 gets final product.
Obtain ternary material through said method processing of the present invention, the untreated ternary material of comparing, when being used to make lithium ion battery, can promote battery capacity and cycle performance, under high voltage, have good electrochemical especially as anode material for lithium-ion batteries.Procedure of the present invention is simple, is convenient to large-scale production.
In conjunction with the accompanying drawings the present invention is described in further detail below by embodiment.
Embodiment 1
Accurately take by weighing 200g LiNi
0.4Co
0.2Mn
0.4O
2The ternary powder body material adds an amount of water and is adjusted to the mud shape, and configuration concentration is the ammonia spirit of 10mol/L, under continuous condition of stirring with 200gLiNi
0.4Co
0.2Mn
0.4O
2The pH value of suspension-turbid liquid is adjusted to 11.0, makes mixture become strong basicity, accurately takes by weighing 20g Co (NO
3)
2It is 10mol/L that solution is regulated its concentration value, under continuous stirring condition, cobalt salt solution is progressively added the LiNi that regulates
0.4Co
0.2Mn
0.4O
2Suspension-turbid liquid.When cobalt salt solution is added to LiNi fully
0.4Co
0.2Mn
0.4O
2In the time of in the suspension-turbid liquid, in room temperature, constantly sustained response was dried the predecessor of prepared in reaction after 5 hours under the condition of stirring in 100-150 ℃ baking oven.Accurately take by weighing the 2.5gLiOH powder at last, predecessor and LiOH powder after the oven dry are mixed be placed in the Muffle furnace, under the air atmosphere, calcination temperature is 850 ℃, and calcination 9 hours reaction is down finished, and obtaining finally is LiCoO
2The LiNi that coats
0.4Co
0.2Mn0
.4O
2The ternary powder body material.Material by this method preparation has excellent electrochemistry cycle performance under the high voltage situation.
Embodiment 2
Accurately take by weighing 200g LiNi
0.4Co
0.2Mn
0.4O
2The ternary powder body material adds an amount of water and is adjusted to the mud shape, and configuration concentration is the ammonia spirit of 10mol/L, under continuous condition of stirring with 200gLiNi
0.4Co
0.2Mn
0.4O
2The pH value of suspension-turbid liquid is adjusted to 11.0, makes mixture become strong basicity, accurately takes by weighing 27.5g Co (NO
3)
2It is 10mol/L that solution is regulated its concentration value, under continuous stirring condition, cobalt salt solution is progressively added the LiNi that regulates
0.4Co
0.2Mn
0.4O
2Suspension-turbid liquid.When cobalt salt solution is added to LiNi fully
0.4Co
0.2Mn
0.4O
2In the time of in the suspension-turbid liquid, in room temperature, constantly sustained response was dried the predecessor of prepared in reaction after 5 hours under the condition of stirring in 100-150 ℃ baking oven.Accurately take by weighing 5.6gLi at last
2CO
3Powder is with predecessor and the Li after the oven dry
2CO
3Powder mixes and is placed in the Muffle furnace, and under the air atmosphere, calcination temperature is 850 ℃, and calcination was reacted down and finished in 9 hours, obtained finally being LiCoO
2The LiNi that coats
0.4Co
0.2Mn
0.4O
2The ternary powder body material.Material by this method preparation has excellent electrochemistry cycle performance under the high voltage situation.
Embodiment 3
Accurately take by weighing 200g LiNi
0.5Co
0.3Mn
0.2O
2The ternary powder body material adds an amount of water and is adjusted to the mud shape, and configuration concentration is the LiOH solution of 10mol/L, under continuous condition of stirring with 200gLiNi
0.5Co
0.3Mn
0.2O
2The pH value of suspension-turbid liquid is adjusted to 11.0, makes mixture become strong basicity, accurately takes by weighing 20g Co (NO
3)
2It is 10mol/L that solution is regulated its concentration value, under continuous stirring condition, cobalt salt solution is progressively added the LiNi that regulates
0.5Co
0.3Mn
0.2O
2Suspension-turbid liquid.When cobalt salt solution is added to LiNi fully
0.5Co
0.3Mn
0.2O
2In the time of in the suspension-turbid liquid, in room temperature, constantly sustained response was dried the predecessor of prepared in reaction after 5 hours under the condition of stirring in 100-150 ℃ baking oven.Accurately take by weighing the 2.0gLiOH powder at last, predecessor and LiOH powder after the oven dry are mixed be placed in the Muffle furnace, under the air atmosphere, calcination temperature is 850 ℃, and calcination 9 hours reaction is down finished, and obtaining finally is LiCoO
2The LiNi that coats
0.5Co
0.3Mn
0.2O
2The ternary powder body material.Material by this method preparation has excellent electrochemistry cycle performance under the high voltage situation.
Embodiment 4
Accurately take by weighing 200g LiNi
0.5Co
0.3Mn
0.2O
2The ternary powder body material adds an amount of water and is adjusted to the mud shape, and configuration concentration is the LiOH solution of 10mol/L, under continuous condition of stirring with 200gLiNi
0.5Co
0.3Mn
0.2O
2The pH value of suspension-turbid liquid is adjusted to 11.5, makes mixture become strong basicity, accurately takes by weighing 11g Co (NO
3)
2It is 10mol/L that solution is regulated its concentration value, under continuous stirring condition, cobalt salt solution is progressively added the LiNi that regulates
0.5Co
0.3Mn
0.2O
2Suspension-turbid liquid.When cobalt salt solution is added to LiNi fully
0.5Co
0.3Mn
0.2O
2In the time of in the suspension-turbid liquid, in room temperature, constantly sustained response was dried the predecessor of prepared in reaction after 5 hours under the condition of stirring in 100-150 ℃ baking oven.Accurately take by weighing 2.0gLi at last
2CO
3Powder is with predecessor and the Li after the oven dry
2CO
3Powder mixes and is placed in the Muffle furnace, and under the air atmosphere, calcination temperature is 850 ℃, and calcination was reacted down and finished in 9 hours, obtained finally being LiCoO
2The LiNi that coats
0.5Co
0.3Mn
0.2O
2The ternary powder body material.Material by this method preparation has excellent electrochemistry cycle performance under the high voltage situation.
Fig. 1-Fig. 4 is by the X-ray diffraction spectrogram of material among embodiment 1, embodiment 2, embodiment 3 and the embodiment 4 of the present invention's preparation, passes through LiCoO from spectrogram as can be seen
2Surface-treated LiNi
xCo
yMn
zO
2In the material, because LiCoO
2Thereby the relatively low agent structure that does not influence material of the content of material, its XRD spectra and untreated LiNi
xCo
yMn
zO
2The spectrogram of material is close, but also a spot of as can be seen LiCoO
2The XRD spectra of material.
Adopt the inventive method gained LiCoO
2Surface-treated LiNi
xCo
yMn
zO
2The process of material battery anode slurry is identical with battery anode slurry process in the prior art.
With embodiment 1 gained LiCoO
2Surface-treated LiNi
0.4Co
0.2Mn
0.4O
2Material and Super P, PVDF prepare anode sizing agent according to the ratio of 80: 15: 5 (mass ratio), after mixing with machine,massing, and slurry on small-sized tensile pulp machine, pole piece uses aluminium foil (thickness 16 μ m), and the slurry surface density is 8-9mg/cm
2As to electrode, EC, EMC, DMC dissolve in the LiPF of 1mol/L at 1: 1: 1 according to volume ratio with metal Li
6In make electrolyte, be full of argon shield and H
2O, O
2All be assembled into half-cell in the glove box less than 1ppm.Half-cell is carried out the experiment of constant current charge and discharge cycle with 0.1C, and charging is by voltage 4.2V, and discharge is by voltage 3.0V.
Embodiment 2, embodiment 3, embodiment 4, gained LiCoO
2Surface-treated LiNi
xCo
yMn
zO
2Material also respectively according to said process assembling half-cell, carries out the experiment of constant current charge and discharge cycle to half-cell under above-mentioned same condition.
Charge and discharge cycle experimental result such as Fig. 5, Fig. 6 and shown in Figure 7.
Fig. 5 is two kinds of different ternary powder body material LiNi
0.4Co
0.2Mn
0.4O
2And LiNi
0.5Co
0.3Mn
0.2O
2At the cyclic curve of high voltage, as we can see from the figure, under high voltage (3.0-4.3V), the cycle performance of two kinds of materials is all poor, LiNi
0.4Co
0.2Mn
0.4O
2Material is with respect to LiNi
0.5Co
0.3Mn
0.2O
2Capability retention relatively low.
Among the figure-6, the full battery of embodiment 1 gained material is cycle charging capacity 1136.1mAh/g first, and discharge capacity is 1011.2mAh, and first charge-discharge efficiency reaches 89%; The full battery of embodiment 2 gained materials is cycle charging capacity 1153.2mAh first, and discharge capacity is 1026.4mAh, and first charge-discharge efficiency reaches 89%.Both first circle efficient is comparatively approaching.Wherein undressed LiNi
0.4Co
0.2Mn
0.4O
2Material is beginning decay rapidly about 100 circles, decays to 300mAh rapidly from initial 1400mAh, capability retention less than 30% through 150 circulation back capacity.And through the material of the embodiment 1 that handled and embodiment 2 through 150 circulations afterwards capability retentions still remain on about 95% after circulating through 200 times all up to 96%, cycle performance is far above untreated material under its high voltage.
Among the figure-7, the full battery of embodiment 2 gained materials is cycle charging capacity 1148.1mAh/g first, and discharge capacity is 1010.3mAh, and first charge-discharge efficiency reaches 88%; The full battery of embodiment 2 gained materials is cycle charging capacity 1149.9mAh first, and discharge capacity is 1009.6mAh, and first charge-discharge efficiency reaches 88%.Both first circle efficient is comparatively approaching.Wherein undressed LiNi
0.5Co
0.3Mn
0.2O
2Material is beginning decay rapidly about 100 circles, decays to 540mAh rapidly from initial 1013mAh, capability retention less than 50% through 200 circulation back capacity.After 250 circulations, capability retention less than 30%, and through the material of the embodiment 3 that handled and embodiment 4 through 200 circulations afterwards capability retentions still remain on about 95% after circulating through 200 times all up to 96%, cycle performance is far above untreated material under its high voltage.
From figure-5, figure-6 and figure-7 adopt the LiCoO of the inventive method gained as can be known
2Surface-treated LiNi
xCo
yMn
zO
2Material has the excellent charging and discharging cycle performance under the high voltage operation environment, simultaneously, the performance of the gram volume of material also gets a promotion greatly under high voltage.
Above content be in conjunction with concrete execution mode to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. ternary material processing method, described ternary material is LiNi
xCo
yMn
zO
2, x+y+z=1, described method comprises,
A, the ternary material powder added add alkaline solution behind the water furnishing pulpous state and regulate the pH value to 8.0-12.0;
B, in the product of steps A, add the solubility cobalt salt solution and fully react;
Add lithium salts after C, the product oven dry, in 500-1000 ℃ of abundant calcination with step B;
The addition of step B cobalt salt and step C lithium salts is according to the LiCoO that generates
2Account for LiCoO
2Add with the ratio of ternary material gross mass 1%～10%.
2. ternary material processing method according to claim 1 is characterized in that: the addition of step B cobalt salt and step C lithium salts is according to the LiCoO that generates
2Account for LiCoO
2Add with the ratio of ternary material gross mass 3%～7%.
3. ternary material processing method according to claim 1 and 2 is characterized in that: in the steps A, described alkaline solution is ammoniacal liquor or the LiOH solution of concentration 1-10mol/L.
4. ternary material processing method according to claim 1 and 2 is characterized in that: in the steps A, regulate the pH value to 10.0-12.0.
5. ternary material processing method according to claim 1 and 2 is characterized in that: among the step B, described solubility cobalt salt is at least a in acetic acid cobalt salt, citric acid cobalt salt or the nitric acid cobalt salt, and the concentration of described solubility cobalt salt is 1～10mol/L.
6. ternary material processing method according to claim 1 and 2 is characterized in that: among the step B, described abundant reaction is meant was constantly fully reacting 1-5 hour under the condition of stirring.
7. ternary material processing method according to claim 1 and 2 is characterized in that: among the step C, described lithium salts is Li
2CO
3, Li
2At least a among O or the LiOH.
8. ternary material processing method according to claim 1 and 2 is characterized in that: among the step C, the described oven dry under 100～150 ℃ carried out, and described abundant calcination is meant calcination 5-24 hour.
9. handle the ternary material that obtains by any described method of claim 1～8.
10. the method that lifting is the capacity of lithium ion battery and the cycle performance of positive electrode with the ternary material comprises with any described method of claim 1～8 ternary material is handled that described ternary material is LiNi
xCo
yMn
zO
2, x+y+z=1.
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| HK12103499.6A HK1163351A1 (en) | 2010-05-07 | 2012-04-10 | Treatment method for ternary material and method for improving capacity and cycle performance of lithium battery |
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| CN104934571A (en) * | 2015-02-11 | 2015-09-23 | 江苏科捷锂电池有限公司 | Preparation method of ternary cathode material coated with Co and Ti through ball milling |
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| CN110518225A (en) * | 2019-09-09 | 2019-11-29 | 江西中汽瑞华新能源科技有限公司 | A kind of preparation method of lithium ion cell positive composite pole piece |
| WO2023241195A1 (en) * | 2022-06-17 | 2023-12-21 | 宁德新能源科技有限公司 | Positive electrode material, electrochemical apparatus comprising same, and electronic apparatus |
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| HK1163351A1 (en) | 2012-09-07 |
| CN102237518B (en) | 2016-02-10 |
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