CN102569784A - Solid melt method for manufacturing lithium-intercalated layered multielement complex - Google Patents
Solid melt method for manufacturing lithium-intercalated layered multielement complex Download PDFInfo
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- CN102569784A CN102569784A CN2012100000854A CN201210000085A CN102569784A CN 102569784 A CN102569784 A CN 102569784A CN 2012100000854 A CN2012100000854 A CN 2012100000854A CN 201210000085 A CN201210000085 A CN 201210000085A CN 102569784 A CN102569784 A CN 102569784A
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- lithium
- licoo2
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The embodiment of the invention discloses a solid melt method for manufacturing a lithium-intercalated layered multielement complex (Ni, Co and Mn). The method is characterized in that a lot of Mn is used, so that the lithium-intercalated layered multielement complex is relatively cheap; and LiCoO2 cannot be used as an anodic material independently, but through expansion and shrinkage of the LiCoO2, an electrode structure is more stable. In combination of the existing mature technologies of LiCoO2, LiNiO2 and LiMnO2, the LiCoO2, the LiNiO2 and the LiMnO2 are produced independently and prepared into a solid melt (at the solid melt forming temperature of 700 DEG C) according to a certain ratio; the properties of the LiCoO2, the LiNiO2 and the LiMnO2 are complementary; and the prepared anode material is stable in performance. The synthetic solid melt method is a simple method for modifying the LiCoO2 and successfully preparing a multielement (Ni, Co and Mn) layered lithium-intercalated material; the method is reliable, practical and mature and is most applicable to industrial scale production; and the performance of the product is stable.
Description
Technical field
The present invention relates to solid-solution approach production embedding lithium stratiform the multiple element compound (Ni, Co, Mn), is anode material for lithium-ion batteries, belongs to the technical field of lithium ion battery.
Background technology
The extensive uses of portable type electronic product on market such as mobile phone, notebook computer, digital camera, DV, electric tool have driven the fast development of lithium ion battery industry.Though the lithium of cobalt acid at present is still the widest anode material for lithium-ion batteries of application; But Along with people's improves constantly high-energy battery performance expectation value; Its capacity and security performance are difficult to satisfy the demand gradually; The African in recent years in addition monopolization to cobalt resource causes the cobalt valency to skyrocket, and the appearance of cobalt acid lithium substitute is demanded in lithium battery market urgently.In recent years, people develop Ni-Co [1] successively, Co-Mn [2], and Mn-Ni mixed oxidization objects systems such as [3], and the Mn-Ni-Co ternary system becomes battery operated person's research focus especially.Ternary system have specific capacity height, good cycle, security performance good, cheap, advantage such as be easy to synthesize, be acknowledged as one of the most promising cobalt acid lithium substitution material.The Mn-Ni-Co ternary system material preparation method of having reported has: NaOH coprecipitation [4], sodium carbonate coprecipitation [5], oxalate coprecipitation method [6], sol-gal process [7], spray drying process [8], hydroxide mixed-sintering method [9] etc.These methods or synthesis route are long, perhaps can't accurately control proportioning raw materials, perhaps can't produce in batches, all have certain limitation.It is raw material that this patent is attempted with manganese, nickel, cobalt cobalt metal oxide and lithium carbonate separately, and the researching high-temperature solid phase reaction prepares novel anode material LiMn
1-x-yNi
xCo
yO
2Feasibility.
Summary of the invention
The object of the invention overcomes existing some weak point of making the anode material for lithium-ion batteries technology, provides a kind of Mn that can use in a large number to reduce Co and an amount of nickel, remedies LiCoO
2The coefficient of expansion, contraction, make that electrode structure is more stable, properties of product are more stable, safer, the relative low price of manganese.Because advantages such as the high security of the height ratio capacity of fully comprehensive lithium nickelate, cobalt acid lithium excellent cycle performance and LiMn2O4 and low cost; Utilize the methods such as doping, coating and finishing of molecular level to synthesize the collaborative composite positive poles of multielement such as manganese nickel cobalt, because of its good research basis and application prospect become one of Recent study focus.For LiMn
xCo
yNi
1-x-yO
2Material, the ratio of each element has remarkable influence to its performance.The existence of Ni can make LiMn
xCo
yNi
1-x-yO
2Cell parameter a and c value increase respectively, c/ a reduces, unit cell volume increases, and helps to improve the reversible embedding lithium capacity of material.But too much Ni
2+Existence can make the cycle performance variation of material again because of the dislocation phenomenon.Co effectively stable compound layer structure and suppress 3a and mix with the 3b position is cationic; Promptly reduce the cation of Li layer and transition metal layer; Thereby make lithium ion to take off embedding easier, and can improve the conductivity of material and improve its charge-discharge performance; But the ratio with Co increases, and c in the cell parameter and a value reduce (but c/ a value increases) respectively, and unit cell volume diminishes, and causes the reversible embedding lithium capacity of material to descend.And after introducing Mn, except reducing cost significantly, can also effectively improve the security performance of material.
Description of drawings
Fig. 1 is patent of invention solid-solution approach production embedding lithium stratiform the multiple element compound LiCoO
2Base-material charging and discharging curve (current density=0.17mA/cm
2) figure;
Fig. 2 is patent of invention solid-solution approach production embedding lithium stratiform the multiple element compound LiCo
0.30.5O
2(LiNiCoO
2) by base-material＜1＞with＜2＞synthetic product charging and discharging curve (current density=0.17mA/cm
2) figure;
Fig. 3 is patent of invention solid-solution approach production embedding lithium stratiform the multiple element compound LiNiO
2Base-material charging and discharging curve (current density=0.17mA/cm
2) figure;
Fig. 4 is the patent of invention solid-solution approach production embedding ternary layered Li of lithium stratiform the multiple element compound (Ni, Co, Mn) O
2XRD figure.
Embodiment
Solid-solution approach production embedding lithium stratiform the multiple element compound (Ni, Co, Mn) preparation: the oxide with elements such as cobalt, nickel, manganese is a raw material; Mix by a certain percentage with battery-level lithium carbonate; Handle through high-temperature calcination, fragmentation, screening, obtain Li (Mn-Ni-Co) O2 ternary material powder.Particle size distribution with laser particle analyzer (LS230 of U.S. Coulter Corporation) assay products; Crystal phase structure with X-ray diffractometer (the Japanese D/max-rB of company of science) assay products; (FDAC S-3500N) observes its microscopic appearance through scanning electron microscopy.
Adopt manganese, nickel source to make raw material, respectively with cobalt oxide (～5 μ m)) with battery-level lithium carbonate by n (Li): n (Mn): n (Ni): n (Co)=1.10: 1/3: 1/3: 1/3 mixes, and calcines 20 h, obtains ternary system product LiMn for 1000 ℃
1/3Ni
1/3Co
1/3O
2The synthesis mechanism of ternary system material and cobalt acid lithium is similar, and the product granularity depends on raw-material granularities such as manganese, nickel, cobalt to a great extent, and with the size of lithium carbonate own irrelevant (lithium carbonate is melting more than 720 ℃).Manganese, nickel raw material granularity are big more, and the product granularity is big more.This is because nickel oxide raw materials size difference is big, used nickel source Ni granularity and the used immediate cause of cobalt oxide, manganese oxide.More near the cobalt oxide size, it is preferably to make raw material.Therefore, adopt the mixing raw materials effect of D5O μ mn:Mn-3.44, D5O μ mn:Ni-5.82 best, in product, evenly distribute so that guarantee transition metal.Along with temperature improves, existing ternary system product generates in the time of 700 ℃, but reaction also not exclusively, has a large amount of nickel oxide, lithium carbonate, cobalt oxide and manganese oxide to exist; When temperature reaches 800 ℃, dephasigns such as still remaining a certain amount of nickel oxide, manganese oxide and lithium carbonate in the product; When temperature reaches 900 ℃, there has not been dephasign to exist in the product, show as and have " NaFeO
2The LiMn of type layer structure
1/3Ni
1/3Co
1/3O
2Pure phase.See that from the sequencing that each metal oxide disappears the reactivity between several kinds of oxides and the lithium carbonate has following rule: cobalt oxide product>manganese oxide>nickel oxide.Adopt 1000 ℃ of product X RD spectral datas to calculate this LiMn
1/3Ni
1/3Co
1/3O
2The material cell parameter.The cell parameter a of the ternary product that this patent employing solid reaction process obtains and c are all big than cobalt acid lithium, Li (MnNiCo) O
2Crystal and electronic structure carried out a large amount of careful research work, go out Mn, Ni, Co at LiMn according to density of states Theoretical Calculation
1/3Ni
1/3Co
1/3O
2Chemical valence in the crystal is respectively+4 ,+2 ,+3.Compare with Co3+ (0.063nm), the ionic radius of Ni2+ is big (0.069nm), and the ionic radius of Mn4+ less (0.060 nm) is obvious, and the cell parameter of Li (MnNiCo) O2 material is bigger than the sour lithium of cobalt, mainly receives the influence of Ni element.Ni element ion radius is big, has also influenced its diffusion in the solid phase reaction process, and it is minimum that the nickel oxide reactivity is shown as, and central temperature is elevated to 900 ℃ and just disappears.
This patent adopts high-temperature solid phase reaction method to synthesize anode material for lithium-ion batteries LiMn
1/3Ni
1/3Co
1/3O
2Result of study shows: manganese source and the nickel source approaching with the cobalt oxide granularity are the suitable raw materials of solid phase method synthesis of ternary material; 900～1000 ℃ of solid phase synthesis can obtain having Li (MnNiCo) O of desirable layered crystal structure
2Pure phase; N (Li)/n (M)=1.10 o'clock, product physical index and electrical property were all better.This is because excessive lithium carbonate makes solid phase reaction more thorough, and has suppressed " cation mixing " in the product crystal structure, has improved the structural stability of material; The ternary material performance of this patent preparation obviously is superior to certain home made materials, and granularity and tap density and cobalt acid lithium are approaching, shows that high temperature solid-state method is preparation Li (MnNiCo) O
2The effective way of material.
Table 1 reason proportioning is to the influence of product chemical property
The chemical property statistics is seen from table 1: the discharge capacity of high lithium proportioning product is high, and the first charge-discharge coulombic efficiency is high, and 1C discharges 50 all circulation volumes maintenances better; Multiplying power discharging property is excellent. and wherein, the raising of coulombic efficiency and cycle performance can be summed up as that Li is excessive to have suppressed " cation mixing "; Improved the stability that Li+ deviates from the back crystal structure, dry straight, after this patent lithium proportioning increases; The capacity performance is better, and this possibly be the solid phase high temperature synthetic reaction for this research, and the lithium carbonate consumption is big; Can impel reaction to carry out more thoroughly, product LiMn
1/3Ni
1/3Co
1/3O
2Crystal structure is more perfect.
Positive electrode is made:
Base-material one: LiCoO
2Synthetic employing raw material cobaltosic oxide: lithium carbonate=820g:380g after fully mixing, places 800 ℃ of the inherent air of Muffle furnace, products such as calcining 12h natural cooling.
Base-material two: LiNiO
2Synthetic employing raw material nickel oxide or nickel hydroxide: lithium carbonate=1:1 (mol ratio), after fully mixing, place in the Muffle furnace first section at 600 ℃ of calcinings of air 6h, second section in air 800 ℃, the 12h natural cooling gets product.
Base-material three: LiMnO
2Synthetic employing raw material manganese dioxide: lithium carbonate=1:1 after fully mixing, places in the Muffle furnace 800 ℃, products such as 12h natural cooling.
Modulate solid solution to the three with any than row, transfer to ratio 0.1 (Co), 0.2 (Ni), 0.7 (Mn) acquisition ternary Li (Ni
1/3Co
1/3Mn
1/3) O
2Product, be optimal dose product property optimum (stability is high, cyclicity best).
Battery is made and is detected: ternary material powder and Kynoar, carbon black, the N-methyl pyrrolidone of preparation are pressed the proper proportion mixing, evenly be coated on the aluminium foil, constitute anode pole piece.Delanium and butadiene-styrene rubber, CMC, deionized water are pressed the proper proportion mixing, evenly be coated on the Copper Foil, constitute cathode pole piece.Make electrolyte with 1mol/LLiPF6/EC+DMC+ EMC (1: 1: 1), process lithium ion battery.To 4.2V, constant voltage charge is to 0.01C again with the battery 1C of the elder generation constant current charge that changes into, and 1C discharges into 2.75V afterwards; So cycle charge discharge is more than 100 times.The battery that is used for the test of hot case needs through 3～5 charge and discharge cycles, and the 1C constant current charge is to 4.2V again, and constant voltage charge places 150 ℃ of baking ovens to 0.01C, and phenomenons such as breach, on fire or blast do not take place in the 60min in timing, are through testing.
Claims (5)
1. the solid solution method is applicable to stratiform LiCoO
2, LiNiO
2, LiMnO
2, be optimal dose product property optimum (stability height, cyclicity best) with arbitrary proportion modulation solid solution, modulation ratio row 0.1 (Co), 0.2 (Ni), 0.7 (Mn).
2. synthetic LiCoO
2, LiNiO
2, LiMnO
2The three has maturation process production to use.
3. should mend three's performance is a kind of positive pole material of stable performance.
4. after the three formed solid solution, inexpensive, safety was to substitute LiCoO
2Optimal material.
5. produce LiCoO respectively
2, LiNiO
2, LiMnO
2The back generates solid solution (700 ℃ of solid solution formation temperatures) with certain proportion.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369660A (en) * | 2007-08-15 | 2009-02-18 | 德固赛（中国）投资有限公司 | Complex particle material for electrode, electrode plate and their production method |
| CN101878556A (en) * | 2007-11-12 | 2010-11-03 | 株式会社杰士汤浅国际 | Active material for lithium rechargeable battery, lithium rechargeable battery, and process for producing the same |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369660A (en) * | 2007-08-15 | 2009-02-18 | 德固赛（中国）投资有限公司 | Complex particle material for electrode, electrode plate and their production method |
| CN101878556A (en) * | 2007-11-12 | 2010-11-03 | 株式会社杰士汤浅国际 | Active material for lithium rechargeable battery, lithium rechargeable battery, and process for producing the same |
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Application publication date: 20120711 |