CN105932232B - A kind of LiMn2O4 composite material and preparation method - Google Patents
A kind of LiMn2O4 composite material and preparation method Download PDFInfo
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Abstract
The present invention discloses a kind of LiMn2O4 composite material and preparation method, and preparation method of the present invention has the advantage that 1) brine lithium resource that comprehensive utilization is natural is as lithium source, reduces the usage amount of refined lithium salt, materials synthesis cost is greatly reduced；2) ion-exchange is uniformly distributed lithium source, manganese source in atomic level, the rearrangement of lattice matrix is easily realized by short-range diffusion, low energy consumption for synthesis process, shows as lower synthesis temperature, shorter generated time；Even particle size distribution reduces polarization.3) constituent content that lithium, magnesium are rationally controlled by deploying pH value prepares lithium position and mixes magnesium types LiMn2O4, improves the average valence of manganese in charge and discharge process, effectively inhibits Jahn-Teller effect, improves cyclical stability.4) there is bigger superiority than other schemes from economy and environmental protection consideration, lithium synthesis composite battery material is especially mentioned from high Mg/Li ratio liquid brine lithium resource has practical significance.
Description
Technical field
The present invention relates to field of lithium ion battery more particularly to a kind of LiMn2O4 composite material and preparation methods.
Background technique
LiMn2O4 is one of more promising lithium ion anode material, is had compared to positive electrodes, LiMn2O4s such as cobalt acid lithiums
Resourceful, at low cost, pollution-free, the advantages that safety is good, good rate capability, be ideal power battery anode material, but
Its poor cycle performance and electrochemical stability but greatly limit its extensive use.Surface modification and doping can be effectively modified
Its chemical property, surface modification can effectively inhibit the dissolution and electrolyte decomposition of manganese；Charge and discharge can be effectively suppressed in doping
Jahn-Teller effect in journey.Surface modification is combined to the chemical property that undoubtedly can be further improved material, manganese with doping
The shortcomings that sour lithium poor circulation, there has been very big change.
Currently, the Industrialized synthesis method of lithium manganate having spinel structure is still based on high temperature solid-state method, mainly with EMD and carbonic acid
Lithium is raw material, cooperates corresponding additive, by mixing, firing, post-processing and etc. and produce.Solid phase reaction is spread
Process control, the excessively high not only energy consumption of synthesis temperature is high, but also the volatilization of lithium is easily caused to be lost, to make up this loss synthesis in solid state
In mostly use rich lithium component design, such as excess 5%wt, cause the raising of cost of material；In addition temperature is excessively high causes to reunite seriously,
Size distribution is uneven, granularity is big, internal resistance is big, polarization is big.And what lithium source used in conventional synthesis technology is battery grade lithium
Salt, it is expensive.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of LiMn2O4 composite material and its preparations
Method, it is intended to solve in existing synthesis technology there are high production cost, reunite serious, size distribution is uneven, granularity is big, internal resistance
Greatly, polarize big problem.
Technical scheme is as follows:
A kind of preparation method of LiMn2O4 composite material, wherein comprising steps of
A, first by λ-MnO2It immerses in pickle after handling, filtering is then added in high Mg/Li ratio natural bittern lithium, makes
λ-MnO2By the lithium in ion exchange adsorption high Mg/Li ratio natural bittern lithium, in Sync enrichment high Mg/Li ratio natural bittern lithium
Then magnesium ion is filtered, washed, dries；
B, then add lithium salts, allotment lithium and magnesium mole: manganese molar ratio is 1:2, is obtained finally by solid-phase sintering
Li1-xMgx Mn2O4LiMn2O4 composite material, wherein x≤0.05.
The preparation method of the LiMn2O4 composite material, wherein in step A, the high Mg/Li ratio natural bittern lithium is
High Mg/Li ratio natural bittern lithium after adjusting pH value by microcosmic salt acid buffer.
The preparation method of the LiMn2O4 composite material, wherein in step A, the diluted acid be dilute hydrochloric acid, dust technology,
One of dilute sulfuric acid, diluted hydrofluoric acid.
The preparation method of the LiMn2O4 composite material, wherein in step B, the lithium salts is lithium carbonate, hydroxide
One or more of lithium, lithium nitrate.
The preparation method of the LiMn2O4 composite material, wherein in step B, the sintering temperature of sintering is 680 DEG C, is burnt
The knot time is 12h.
The preparation method of the LiMn2O4 composite material, wherein in step B, x=0.02.
A kind of LiMn2O4 composite material, wherein using the preparation method system of as above any LiMn2O4 composite material
It is standby to form.
The utility model has the advantages that raw material sources of the present invention are at a low price, low energy consumption for preparation process, and epigranular, and polarization resistance is small, has
Better high rate performance and cycle performance.
Specific embodiment
The present invention provides a kind of LiMn2O4 composite material and preparation method, for make the purpose of the present invention, technical solution and
Effect is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein
It is only used to explain the present invention, be not intended to limit the present invention.
The present invention provides a kind of preparation method of LiMn2O4 composite material, wherein comprising steps of
A, first by λ-MnO2It immerses in pickle after handling, filtering is then added in high Mg/Li ratio natural bittern lithium, makes
λ-MnO2By the lithium in ion exchange adsorption high Mg/Li ratio natural bittern lithium, in Sync enrichment high Mg/Li ratio natural bittern lithium
Then magnesium ion is filtered, washed, dries, obtains powder；
B, lithium salts, allotment lithium and magnesium mole are then added in powder: manganese molar ratio is 1:2, is burnt finally by solid phase
Knot obtains Li1-xMgx Mn2O4LiMn2O4 composite material, wherein x≤0.05.
The present invention reduces the use of refined lithium salt using natural high Mg/Li ratio natural bittern lithium resource as lithium source
Amount, materials synthesis cost reduce.At a low price, low energy consumption for preparation process, and epigranular, after in-stiu coating for raw material sources of the present invention
Polarization resistance is small, there is better high rate performance and cycle performance.
Preferably, in step A, the high Mg/Li ratio natural bittern lithium is the height adjusted after pH value by microcosmic salt acid buffer
Mg/Li ratio natural bittern lithium.The present invention adjusts pH value by microcosmic salt acid buffer, can rationally control the constituent content of magnesium, prepares
The LiMn2O4 composite material of magnesium is mixed in lithium position, improves the average valence of manganese in charge and discharge process, effectively inhibits Jahn-Teller effect
It answers, improves cyclical stability.It is highly preferred that the high Mg/Li ratio natural bittern lithium is to pass through disodium hydrogen phosphate-sodium dihydrogen phosphate
High Mg/Li ratio natural bittern lithium after adjusting pH value, to further increase cyclical stability.
Preferably, in step A, the diluted acid can be but be not limited to dilute hydrochloric acid, dust technology, dilute sulfuric acid, in diluted hydrofluoric acid
One kind.
Preferably, Li1-xMgxFePO4In, x=0.02, to further increase the performance of LiMn2O4 composite material.Preferably,
The sintering temperature of sintering is 680 DEG C, and sintering time 12h is sintered under this condition, and LiMn2O4 composite material obtained has more
High cycle performance.
Preferably, lithium salts of the present invention one of can be but be not limited to lithium carbonate, lithium hydroxide, lithium nitrate or several
Kind.
The present invention is also described in detail the preparation method of LiMn2O4 composite material, specifically includes that steps are as follows:
Step S1: by a certain amount of λ-MnO2Powder, which is placed in the dilute acid soln of 0.01-0.1M, handles 6-8h, filtering, standby
With；
Step S2: high Mg/Li ratio natural bittern lithium is adjusted to through 0.02-0.1M disodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution
PH is 6.0-8.0, by treated in S1 λ-MnO2Powder is placed in lidded container, injects the high Mg/Li ratio day of deployed pH value
Right brine lithium, gets togather lid, shakes 4-12h；
Step S3: it is filtered, washed, 100-150 DEG C of processing 2-6h drying, tests lithium, content of magnesium；
Step S4: according to lithium, the content of magnesium in S3, weighing lithium salts, and make the mole of lithium and magnesium: manganese molar ratio 1:2 is obtained
Obtain mixture；
Step S5: the mixture ball milling 2-4h of S4 is uniformly mixed；
Step S6: by the mixture in S5 after mixing in Muffle furnace, 550-700 DEG C of sintering processes 10-24h is obtained
To Li1-xMgxMn2O4(x≤0.05).
The above-mentioned preparation method of the present invention has the advantage that
1) comprehensive utilization high Mg/Li ratio natural bittern lithium resource reduces the usage amount of refined lithium salt, material as lithium source
Synthesis cost is greatly reduced.
2) ion-exchange is uniformly distributed lithium source, manganese source in atomic level, easily realizes lattice square by short-range diffusion
The rearrangement of battle array, low energy consumption for synthesis process, shows as lower synthesis temperature, shorter generated time；Even particle size distribution reduces
Polarization.
3) constituent content that lithium, magnesium are rationally controlled by deploying pH value prepares lithium position and mixes magnesium types LiMn2O4, improves charge and discharge
The average valence of manganese in the process effectively inhibits Jahn-Teller effect, improves cyclical stability.
4) there is bigger superiority than other schemes from economy and environmental protection consideration, especially from high Mg/Li ratio liquid halogen
Lithium synthesis composite battery material is mentioned in water lithium resource has practical significance.
The present invention also provides a kind of LiMn2O4 composite materials, wherein using as above any LiMn2O4 composite material
Preparation method be prepared.LiMn2O4 composite material epigranular of the present invention, polarization resistance is small, have better high rate performance and
Cycle performance.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
Taking 1L amount containing lithium is the high Mg/Li ratio natural bittern lithium of 1100mg/L, and wherein magnesium lithium mass ratio is 45.32, warp
It is 6.0 that 0.02M disodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, which is adjusted to pH,.Weigh 174g λ-MnO2Powder is placed in dilute salt of 0.01M
6h is handled in acid solution, filtering is placed in lidded container, injects the high Mg/Li ratio natural bittern lithium of deployed pH value, get togather lid
Son shakes 10h, is filtered, washed, after 100 DEG C of drying 6h, measures λ-MnO2Lithium ion exchange rate be 34.7mg/g, magnesium from
The exchange rate of son is 1.38mg/g.According to measure lithium, magnesium amount, supplement 4.72g lithium carbonate so that the mole of lithium and magnesium: manganese
Molar ratio is 1:2, and after ball milling 3h is mixed, 550 DEG C of sintering for 24 hours, obtain doping type lithium manganate composite material in Muffle furnace
Li0.99Mg0.01Mn2O4.LiMn2O4 composite material D50 is 4.2 μm, and size distribution span is 1.7.
Aluminium foil is coated in after above-mentioned LiMn2O4 composite material, conductive carbon, binder are mixed according to the mass ratio of 94:3:3
On prepare pole piece, be to electrode assembling half-cell with lithium, electrolyte is the LiFPF of 1mol/L6/DC+EC+DMC.Electric performance test
As a result are as follows: 0.1C capacity 119mAh/g for the first time, capacity 97.5mAh/g after circulation 100 times, capacity retention ratio 81.9%；1C capacity
102 mAh/g；2C capacity 95.6mAh/g.
Embodiment 2
Taking 1L amount containing lithium is the high Mg/Li ratio natural bittern lithium of 500mg/L, and wherein magnesium lithium mass ratio is 36, through 0.05M phosphorus
It is 8.0 that sour disodium hydrogen-phosphate sodium dihydrogen buffer solution, which is adjusted to pH,.Weigh 174g λ-MnO2Powder is placed in 0.05 dilution heat of sulfuric acid
6h is handled, filtering is placed in lidded container, injects the high Mg/Li ratio natural bittern lithium of deployed pH value, get togather lid, shakes
12h is filtered, washed, after 120 DEG C of drying 4h, measures λ-MnO2It is 30.9mg/g to lithium ion exchanged rate, to magnesium ion exchange rate
For 2.07mg/g.According to lithium, magnesium amount has been contained, 5.21g lithium hydroxide is supplemented, so that the mole of lithium and magnesium: manganese molar ratio is 1:
After 2, ball milling 2h are mixed, 700 DEG C of sintering 10h, obtain doping type lithium manganate composite material in Muffle furnace
Li0.985Mg0.015Mn2O4.LiMn2O4 composite material D50 is 4.8 μm, and size distribution span is 2.4.
Aluminium foil is coated in after above-mentioned LiMn2O4 composite material, conductive carbon, binder are mixed according to the mass ratio of 94:3:3
On prepare pole piece, be to electrode assembling half-cell with lithium, electrolyte is the LiFPF of 1mol/L6/DC+EC+DMC.Electric performance test
As a result are as follows: 0.1C capacity 116.4mAh/g for the first time, capacity 98.4mAh/g after circulation 100 times, capacity retention ratio 84.5%；1C holds
Measure 103.4 mAh/g.
Embodiment 3
Taking 1L amount containing lithium is the high Mg/Li ratio natural bittern lithium of 1500mg/L, and wherein magnesium lithium mass ratio is 51.3, through 0.05M
It is 7.5 that disodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, which is adjusted to pH,.Weigh 174g λ-MnO2The dust technology that powder is placed in 0.05 is molten
8h is handled in liquid, filtering is placed in lidded container, injects the high Mg/Li ratio natural bittern lithium of deployed pH value, get togather lid,
4h is shaken, is filtered, washed, after 150 DEG C of drying 2h, λ-MnO2It is 29.8mg/g to lithium ion exchanged rate, to magnesium ion exchange rate
For 2.76mg/g.According to lithium, magnesium amount has been contained, 16.52g lithium nitrate is supplemented, so that the mole of lithium and magnesium: manganese molar ratio is 1:2,
After ball milling 4h is mixed, 680 DEG C of sintering 12h, obtain doping type lithium manganate composite L i in Muffle furnace0.98Mg0.02Mn2O4。
LiMn2O4 composite material D50 is 3.7 μm, and size distribution span is 2.1.
Aluminium foil is coated in after above-mentioned LiMn2O4 composite material, conductive carbon, binder are mixed according to the mass ratio of 94:3:3
On prepare pole piece, be to electrode assembling half-cell with lithium, electrolyte is the LiFPF of 1mol/L6/DC+EC+DMC.Electric performance test
As a result are as follows: 0.1C capacity 109.8mAh/g for the first time, capacity 102.8mAh/g after circulation 100 times, capacity retention ratio 93.6%；1C
Capacity 103.1mAh/g.
Embodiment 4
Taking 1L amount containing lithium is the high Mg/Li ratio natural bittern lithium of 1500mg/L, and wherein magnesium lithium mass ratio is 51.3, through 0. 1M
It is 8.0 that disodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, which is adjusted to pH,.Weigh 174g λ-MnO2 powder be placed in 0.1M diluted hydrofluoric acid it is molten
6h is handled in liquid, filtering is placed in lidded container, injects the high Mg/Li ratio natural bittern lithium of deployed pH value, get togather lid,
4h is shaken, is filtered, washed, after 150 DEG C of drying 2h, λ-MnO2It is 33.8mg/g to lithium ion exchanged rate, to magnesium ion exchange rate
For 6.90mg/g.According to lithium, magnesium amount has been contained, 7.58g lithium nitrate is supplemented, so that the mole of lithium and magnesium: manganese molar ratio is 1:2,
After ball milling 3h is mixed, 600 DEG C of sintering 15h, obtain doping type lithium manganate composite L i in Muffle furnace0.95Mg0.05Mn2O4。
LiMn2O4 composite material D50 is 3.2 μm, and size distribution span is 1.8.
Aluminium foil is coated in after above-mentioned LiMn2O4 composite material, conductive carbon, binder are mixed according to the mass ratio of 94:3:3
On prepare pole piece, be to electrode assembling half-cell with lithium, electrolyte is the LiFPF of 1mol/L6/DC+EC+DMC.Electric performance test
As a result are as follows: 0.1C capacity 97.5mAh/g for the first time, capacity 92.4mAh/g after circulation 100 times, capacity retention ratio 94.8%；1C holds
Measure 93mAh/g.
Comparative example 1
According to lithium: magnesium: manganese molar ratio is that 0.98:0.02:2 weighs 174g λ-MnO respectively2Powder, 36.26g lithium carbonate,
2.96g magnesium nitrate, ball milling mix, and 800 DEG C of sintering 20h, obtain the doping type lithium manganate composite wood of synthesis in solid state in Muffle furnace
Expect Li0.98Mg0.02Mn2O4.LiMn2O4 composite material D50 is 10.3 μm, and size distribution span is 4.7.
Aluminium foil is coated in after above-mentioned LiMn2O4 composite material, conductive carbon, binder are mixed according to the mass ratio of 94:3:3
On prepare pole piece, be to electrode assembling half-cell with lithium, electrolyte is the LiFPF of 1mol/L6/DC+EC+DMC.Electric performance test
As a result are as follows: 0.1C capacity 101.7mAh/g for the first time, capacity 82.7mAh/g after circulation 100 times, capacity retention ratio 81.3%；1C holds
Measure 93.2 mAh/g.
In conclusion a kind of LiMn2O4 composite material and preparation method provided by the invention, preparation method tool of the present invention
There is following advantage: 1) comprehensively utilizing natural brine lithium resource as lithium source, reduce the usage amount of refined lithium salt, materials synthesis
Cost is greatly reduced；2) ion-exchange is uniformly distributed lithium source, manganese source in atomic level, is easily realized by short-range diffusion brilliant
The rearrangement of lattice matrix, low energy consumption for synthesis process, shows as lower synthesis temperature, shorter generated time；Even particle size distribution,
Reduce polarization.3) constituent content that lithium, magnesium are rationally controlled by deploying pH value prepares lithium position and mixes magnesium types LiMn2O4, improves charge and discharge
The average valence of manganese in electric process effectively inhibits Jahn-Teller effect, improves cyclical stability.4) it is protected from economy and environment
Shield considers there is bigger superiority than other schemes, and it is compound that lithium synthesis is especially proposed from high Mg/Li ratio liquid brine lithium resource
Battery material has practical significance.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (7)
1. a kind of preparation method of LiMn2O4 composite material, which is characterized in that comprising steps of
A, first by λ-MnO2It immerses in pickle after handling, filtering is then added in high Mg/Li ratio natural bittern lithium, makes λ-
MnO2Magnesium by the lithium in ion exchange adsorption high Mg/Li ratio natural bittern lithium, in Sync enrichment high Mg/Li ratio natural bittern lithium
Then ion is filtered, washed, dries；
B, then add lithium salts, allotment lithium and magnesium mole: manganese molar ratio is 1:2, obtains Li finally by solid-phase sintering1-xMgx
Mn2O4LiMn2O4 composite material, wherein x≤0.05；
The sintering temperature of the solid-phase sintering is 550-700 DEG C.
2. the preparation method of LiMn2O4 composite material according to claim 1, which is characterized in that in step A, the high magnesium
Lithium is than the high Mg/Li ratio natural bittern lithium that natural bittern lithium is after adjusting pH value by microcosmic salt acid buffer.
3. the preparation method of LiMn2O4 composite material according to claim 1, which is characterized in that in step A, the diluted acid
For one of dilute hydrochloric acid, dust technology, dilute sulfuric acid, diluted hydrofluoric acid.
4. the preparation method of LiMn2O4 composite material according to claim 1, which is characterized in that in step B, the lithium salts
For one or more of lithium carbonate, lithium hydroxide, lithium nitrate.
5. the preparation method of LiMn2O4 composite material according to claim 1, which is characterized in that in step B, the burning of sintering
Junction temperature is 680 DEG C, sintering time 12h.
6. the preparation method of LiMn2O4 composite material according to claim 1, which is characterized in that in step B, x=0.02.
7. a kind of LiMn2O4 composite material, which is characterized in that using the LiMn2O4 composite material as described in claim 1 ~ 6 is any
Preparation method be prepared.
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| CN102049238A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN105506310A (en) * | 2016-01-07 | 2016-04-20 | 李震祺 | Method for extracting lithium from lithium-containing brine |
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| CN102049238A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Ion sieve for selectively extracting lithium and application thereof |
| CN105506310A (en) * | 2016-01-07 | 2016-04-20 | 李震祺 | Method for extracting lithium from lithium-containing brine |
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| 从盐湖卤水中提取锂的吸附技术;董茜等;《盐业与化工》;20070625;第36卷(第3期);31-34页 |
| 尖晶石型Li1-xMgxMn2O4正极材料的制备和性质;姚经文等;《材料导报》;20070716;第21卷(第6期);144-146页 |
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