CN100502107C - Method for producing lithium ion battery anode material LiNi1-xCoxO2 - Google Patents

Method for producing lithium ion battery anode material LiNi1-xCoxO2 Download PDF

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CN100502107C
CN100502107C CNB2007101214934A CN200710121493A CN100502107C CN 100502107 C CN100502107 C CN 100502107C CN B2007101214934 A CNB2007101214934 A CN B2007101214934A CN 200710121493 A CN200710121493 A CN 200710121493A CN 100502107 C CN100502107 C CN 100502107C
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CN101118966A (en
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聂祚仁
席晓丽
宋顺林
王志宏
左铁镛
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Beijing University of Technology
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Abstract

The present invention relates to a producing method used for producing lithium ion battery positive pole material LiNi1-xCoxO2, which belongs to the technical field of battery material production. The producing method comprises the flowing steps: measuring and fetching raw material by a corresponding mol ratio according to the molecular formula of the lithium ion battery positive material; making the raw material up into mixing pellucid Li-Ni-Co salt solution with the density of 0.1 to 1 mol per l; distributing the mixed salt solution in the liquid nitrogen to pre-cooling; placing the cooling object in a freeze dryer to dry in vacuum to get a precursors; calcining the dried precursors for three times in air condition then the supermicro lithium ion battery positive material LiNi1-xCoxO2 can be gained. The present invention has simple art procedure, and the calcine temperature is low while calcining takes a short time and the powder gained convert less while shape uniformly. The granularity is 100um to 350 um, and the product has favorable electrochemical characters.

Description

A kind of anode material for lithium-ion batteries LiNi 1-xCo xO 2The preparation method
Technical field
A kind of anode material for lithium-ion batteries LiNi 1-xCo xO 2The preparation method, belong to the battery material technical field.
Background technology
Lithium ion battery is after Ni-MH battery, the new generation of green chargeable battery that countries in the world are competitively developed and developed, it has operating voltage height, in light weight, characteristics such as specific energy is big, self-discharge rate is little, have extended cycle life, memory-less effect, environmental pollution are little, is the ideal source of electronic installation miniaturization ands such as video camera, mobile phone, notebook computer and Portable Measurement Instrument and environmental-protecting type electric automobile.Since Japan succeeded in developing lithium ion battery and put on market nineteen ninety, because of its particular performances forms one Study on Li-ion batteries using upsurge at home and abroad.In the lithium ion battery with the charcoal material as cathode, positive electrode serves as the effect of lithium ion source, not only will be provided between the both positive and negative polarity lithium intercalation compound back and forth embedding and take off needed lithium ion, forms the needed lithium of SEI film but also will bear the negative material surface; Moreover the actual capacity of positive electrode is on the low side, so the useful load of positive electrode is more much bigger than negative pole in the battery.LiNi 1-xCo xO 2Compound has higher reversible capacity, can utilize its formation for negative pole SEI film that Li is provided the source, reduces anodal extra useful load, thereby improves battery capacity.Positive electrode LiNi in addition 1-xCo xO 2Easily synthetic, stable performance, thereby be with a wide range of applications.
The synthetic method of anode material for lithium-ion batteries is a lot, roughly is divided into the low-temperature synthetic method of high temperature solid-state method and " softening learning ", as coprecipitation, sol-gel processing, spray drying process etc.Traditional synthetic method adopts high temperature solid-state method more, because LiNiO 2The synthesis condition harshness, solid phase synthesis process temperature height, the time is long, very easily causes the generation that lacks the lithium phenomenon, and material property is worsened.For this reason, people are to LiNi 1-xCo xO 2The research of solid solution focuses on solid solution degree, the aspects such as uniformity of material on microstructure of material more.
Summary of the invention
The purpose of this invention is to provide a kind of preparation anode material for lithium-ion batteries LiNi 1-xCo xO 2Method, its technology is very simple, and is low for equipment requirements, raw material cheaply is easy to get.
A kind of anode material for lithium-ion batteries LiNi 1-xCo xO 2The preparation method, it is characterized in that it may further comprise the steps:
(1) with hydroxide nickel (OH) 2, cobalt oxalate [CoC 2O 42H 2O] crystal powder is dissolved in the ammoniacal liquor nickel that must clarify, cobalt ammonia complex solution, nickel hydroxide, cobalt oxalate [CoC respectively 2O 42H 2O] both mol ratio is according to Li:(Ni, Co)=1.1～1.2:1; Ni:Co=1～0.7:0～0.3, both are mixed clarification after, in mixed solution, add lithium oxalate solution again, be mixed with the Li-Ni-Co clarification mixing salt solution of 0.1～1mol/L;
(2) use the nitrogen spray gun, above-mentioned mixing salt solution is dispersed in pre-freeze in the liquid nitrogen;
(3) scars after the pre-freeze in the above-mentioned liquid nitrogen are placed freeze dryer carry out vacuumize to obtain before
Drive body;
(4) above-mentioned dried presoma is carried out oxygen atmosphere calcining down, oxygen flow is 200 ml/min～300 ml/min, heating rate is 5～15 ℃/min, 180 ℃～250 ℃ insulations 1～2 hour, 400～500 ℃ are incubated 3～4 hours,. be warmed up to 650 ℃～800 ℃ calcinings of high temperature section then, be incubated 5 hours～10 hours and obtain positive electrode LiNi 1-xCo xO 2
Above-mentioned anode material for lithium-ion batteries LiNi 1-xCo xO 2The preparation method advise using hydroxide nickel (OH) 2Fresh sediment for solvable nickel salt and highly basic reaction generation.
The described nitrogen spray gun of step (2), its pressure are 1.5 atmospheric pressure～3.5 atmospheric pressure; The described vacuumize of step (3), wherein the executive program of freeze dryer is: the operating pressure in 0 minute～1000 minutes is that 450 millitorrs, temperature are-20 ℃; Operating pressure in 1000 minutes～3000 minutes is that 300 millitorrs, temperature are-11 ℃; Operating pressure in 3000 minutes～4500 minutes is that 150 millitorrs, temperature are-6 ℃; Operating pressure in 4500 minutes～5300 minutes is that 80 millitorrs, temperature are 0 ℃; Operating pressure in 5300 minutes～5500 minutes is that 5 millitorrs, temperature are 15 ℃.
Wherein the technical parameter of spray gun pressure and freeze-drying program requires and can adjust accordingly according to initial concentration of solution and quantity, and the adjustment of technical parameter is that the prior art personnel are known.
The present invention adopts liquid nitrogen pre-freeze-freeze-drying, can prevent the poly-partially and crystallization of solution component, it is little to obtain amorphous granular precursor degree, and directly solved the even mixed problem of raw material, therefore the temperature and the calcination time of calcination process have subsequently been reduced, reduce the lithium evaporation loss that high-temperature calcination brings, significantly reduced energy consumption, improved product quality.The LiNi for preparing 1-xCo xO 2Powder is reunited less, pattern is even, and granularity is little, can reach 100nm～350nm, and particle size can be by the process conditions adjustment, and the powder crystallization degree is good, has good electrochemistry cycle performance.The anode material for lithium-ion batteries that can be used as various uses.
Below in conjunction with accompanying drawing effect of the present invention is explained as follows.
The complex lithium nickel cobalt oxide LiNi of Fig. 1 under 650 ℃～800 ℃ of different temperatures, making 0.8Co 0.2O 2The XRD diffracting spectrum, as seen from the figure, more than 650 ℃ the calcining after material had α-NaFeO 2Layer structure.
Fig. 2 is synthetic positive electrode LiNi 0.8Co 0.2O 2The image of field emission scanning electron microscope, as seen from the figure, do not have between the powder that adopts the method for liquid nitrogen pre-freeze-freeze drying-air roasting to obtain and reunite, even particle size distribution is about 300nm.
Table 1 is the synthetic LiNi of different calcining heats 0.8Co 0.2O 2Crystal parameters, by the table as seen, the sample I of 750 ℃ of calcinings (003)/ I (104)Be 1.51, R[(I (006)+ I (102))/I (101)] be 0.462, have better six side's layer structures, there is not tangible cation mixing phenomenon.
Hence one can see that, and with the obvious refinement of powder crystal grain of freeze-drying preparation, size reaches nanoscale, and the powder crystallization degree is good, do not have tangible cation mixing phenomenon, this helps lithium ion and embeds and deviate from the stable of material structure in the process, is indicating excellent electrochemical properties.
Description of drawings
Fig. 1: the complex lithium nickel cobalt oxide LiNi that obtains under the different calcining heats 0.8Co 0.2O 2The XRD diffracting spectrum;
Fig. 2: synthetic positive electrode LiNi 0.8Co 0.2O 2The FESEM image of powder;
Embodiment
Example 1: the stoichiometric proportion with Li:Ni (mol ratio)=1.1:1 takes by weighing required raw material, with fresh Ni (OH) 2Be dissolved in the excessive ammonia solution, get blue settled solution, in settled solution, add a certain amount of lithium oxalate solution again, be mixed with the Li-Ni clarification mixing salt solution of 0.1mol/L.Use the nitrogen spray gun, spray gun pressure is 3.5 atmospheric pressure, and the mixed solution of clarifying is dispersed in the liquid nitrogen.Scars with liquid nitrogen frozen place the FTD Dura-stop MP of FTS company type freeze dryer to carry out vacuumize again, and the executive program of freeze dryer is: the operating pressure in 0 minute～1000 minutes is that 450 millitorrs, temperature are-20 ℃; Operating pressure in 1000 minutes～3000 minutes is that 300 millitorrs, temperature are-11 ℃; Operating pressure in 3000 minutes～4500 minutes is that 150 millitorrs, temperature are-6 ℃; Operating pressure in 4500 minutes～5300 minutes is that 80 millitorrs, temperature are 0 ℃; Operating pressure in 5300 minutes～5500 minutes is that 5 millitorrs, temperature are 15 ℃.Adopt oxygen atmosphere calcining down, oxygen flow is 300 ml/min, and heating rate is 10 ℃/min, and 180 ℃ of insulations 2 hours, 400 ℃ were incubated 3 hours, are warmed up to 650 ℃ of calcinings then, are incubated 5 hours, obtain the ultra micro LiNiO about granularity 100nm 2Powder.
Example 2: with Li:(Ni, Co) (mol ratio)=1.1:1; The stoichiometric proportion of Ni:Co (mol ratio)=0.9:0.1 takes by weighing required raw material, respectively with fresh Ni (OH) 2, cobalt oxalate [CoC 2O 42H 2O] crystal powder is dissolved in the excessive ammonia solution, settled solution, in settled solution, add a certain amount of lithium oxalate solution again, be mixed with the Li-Ni-Co clarification mixing salt solution of 0.3mol/L.Use the nitrogen spray gun, spray gun pressure is 1.5 atmospheric pressure, and the mixed solution of clarifying is dispersed in the liquid nitrogen.Scars with liquid nitrogen frozen place the FTD Dura-stop MP of FTS company type freeze dryer to carry out vacuumize again, and the executive program of freeze dryer is: the operating pressure in 0 minute～1000 minutes is that 450 millitorrs, temperature are-20 ℃; Operating pressure in 1000 minutes～3000 minutes is that 300 millitorrs, temperature are-11 ℃; Operating pressure in 3000 minutes～4500 minutes is that 150 millitorrs, temperature are-6 ℃; Operating pressure in 4500 minutes～5300 minutes is that 80 millitorrs, temperature are 0 ℃; Operating pressure in 5300 minutes～5500 minutes is that 5 millitorrs, temperature are 15 ℃.Adopt oxygen atmosphere calcining down, oxygen flow is 260 ml/min, and heating rate is 15 ℃/min, and 200 ℃ of insulations 1.5 hours, 450 ℃ of insulations 4 hours were warmed up to 700 ℃ of calcinings then, are incubated 7 hours, obtains granularity and be the ultra micro LiNi about 160nm 0.9Co 0.1O 2Powder.
Example 3: with Li:(Ni, Co) (mol ratio)=1.2:1; The stoichiometric proportion of Ni:Co (mol ratio)=0.8:0.2 takes by weighing required raw material, respectively with fresh Ni (OH) 2, cobalt oxalate [CoC 2O 42H 2O] crystal powder is dissolved in the excessive ammonia solution, settled solution, in settled solution, add a certain amount of lithium oxalate solution again, be mixed with the Li-Ni-Co clarification mixing salt solution of 1mol/L.Use the nitrogen spray gun, spray gun pressure is 2.5 atmospheric pressure, and the mixed solution of clarifying is dispersed in the liquid nitrogen.Scars with liquid nitrogen frozen place the FTD Dura-stop MP of FTS company type freeze dryer to carry out vacuumize again, and the executive program of freeze dryer is: the operating pressure in 0 minute～1000 minutes is that 450 millitorrs, temperature are-20 ℃; Operating pressure in 1000 minutes～3000 minutes is that 300 millitorrs, temperature are-11 ℃; Operating pressure in 3000 minutes～4500 minutes is that 150 millitorrs, temperature are-6 ℃; Operating pressure in 4500 minutes～5300 minutes is that 80 millitorrs, temperature are 0 ℃; Operating pressure in 5300 minutes～5500 minutes is that 5 millitorrs, temperature are 15 ℃.Adopt oxygen atmosphere calcining down, oxygen flow is 230 ml/min, and heating rate is 10 ℃/min, and 200 ℃ of insulations 1 hour, 500 ℃ of insulations 4 hours were warmed up to 750 ℃ of calcinings then, are incubated 5 hours, obtains granularity and be the ultra micro LiNi about 300nm 0.8Co 0.2O 2Powder.
Example 4: with Li:(Ni, Co) (mol ratio)=1.15:1; The stoichiometric proportion of Ni:Co (mol ratio)=0.7:0.3 takes by weighing required raw material, respectively with fresh Ni (OH) 2, cobalt oxalate [CoC 2O 42H 2O] crystal powder is dissolved in the excessive ammonia solution, settled solution, in settled solution, add a certain amount of lithium oxalate solution again, be mixed with the Li-Ni-Co clarification mixing salt solution of 0.6mol/L.Use the nitrogen spray gun, spray gun pressure is 2.0 atmospheric pressure, and the mixed solution of clarifying is dispersed in the liquid nitrogen.Scars with liquid nitrogen frozen place the FTD Dura-stop MP of FTS company type freeze dryer to carry out vacuumize again, and the executive program of freeze dryer is: the operating pressure in 0 minute～1000 minutes is that 450 millitorrs, temperature are-20 ℃; Operating pressure in 1000 minutes～3000 minutes is that 300 millitorrs, temperature are-11 ℃; Operating pressure in 3000 minutes～4500 minutes is that 150 millitorrs, temperature are-6 ℃; Operating pressure in 4500 minutes～5300 minutes is that 80 millitorrs, temperature are 0 ℃; Operating pressure in 5300 minutes～5500 minutes is that 5 millitorrs, temperature are 15 ℃.Adopt oxygen atmosphere calcining down, oxygen flow is 150 ml/min, and heating rate is 5 ℃/min, and 250 ℃ of insulations 1 hour, 450 ℃ of insulations 4 hours were warmed up to 800 ℃ of calcinings then, are incubated 10 hours, obtains granularity and be the ultra micro LiNi about 350nm 0.7Co 0.3O 2Powder.
With the above-mentioned lithium ion cell positive positive electrode LiNi for preparing 1-xCo xO 2Powder, conductive agent acetylene black, binding agent polyvinylidene fluoride mix by certain mass ratio (85:10:5), be dissolved in the solvent N-methyl pyrrolidone (NMP), mix, be applied on the aluminium foil behind the dry certain hour, with 110 ℃ of oven dry down, make aluminium foil and positive electrode strong bonded then under 15MP pressure, 130 ℃ of following vacuumizes are stayed standby after 12 hours.Adopt three-electrode system that the positive plate for preparing is carried out cyclic voltammetry experiment, auxiliary electrode and reference electrode are the lithium sheet, and electrolyte is 1mol/L LiPF 6EC:DMC (EC:DMC=3:7) mixed liquor, sweep speed is 0.2～1mV/s, the scanning voltage scope is 2.5～4.2V, can draw the anode active material of lithium ion battery LiNi of preparation by cyclic voltammetry experiment at a slow speed 1-xCo xO 2Has good electrochemistry cycle performance.
Table 1: the LiNi that different calcining heats are synthetic 0.8Co 0.2O 2Crystal parameters
Table 1
Figure C200710121493D00071

Claims (3)

1, a kind of anode material for lithium-ion batteries LiNi 1-xCo xO 2The preparation method, it is characterized in that it may further comprise the steps:
(1) with hydroxide nickel (OH) 2, cobalt oxalate [CoC 2O 42H 2O] crystal powder is dissolved in the ammoniacal liquor nickel that must clarify, cobalt ammonia complex solution, nickel hydroxide, cobalt oxalate [CoC respectively 2O 42H 2O] both mol ratio is according to Ni:Co=1～0.7:0～0.3, after both are mixed clarification, again according to mol ratio Li:(Ni, Co)=1.1～1.2:1 adds lithium oxalate solution in mixed solution, be mixed with the Li-Ni-Co clarification mixing salt solution of 0.1～1mol/L;
(2) use the nitrogen spray gun, above-mentioned mixing salt solution is dispersed in pre-freeze in the liquid nitrogen;
(3) scars after the pre-freeze in the above-mentioned liquid nitrogen are placed freeze dryer carry out vacuumize and obtain presoma;
(4) above-mentioned dried presoma is carried out oxygen atmosphere calcining down, oxygen flow is 200 ml/min～300 ml/min, heating rate is 5～15 ℃/min, 180 ℃～250 ℃ insulations 1～2 hour, 400～500 ℃ are incubated 3～4 hours, be warmed up to 650 ℃～800 ℃ calcinings of high temperature section then, be incubated 5 hours～10 hours and obtain positive electrode LiNi 1-xCo xO 2
2, preparation method according to claim 1 is characterized in that: the described nitrogen spray gun of step (2), its pressure are 1.5 atmospheric pressure～3.5 atmospheric pressure.
3, preparation method according to claim 1 is characterized in that: the described vacuumize of step (3), and wherein the executive program of freeze dryer is: the operating pressure in 0 minute～1000 minutes is that 450 millitorrs, temperature are-20 ℃; Operating pressure in 1000 minutes～3000 minutes is that 300 millitorrs, temperature are-11 ℃; Operating pressure in 3000 minutes～4500 minutes is that 150 millitorrs, temperature are-6 ℃; Operating pressure in 4500 minutes～5300 minutes is that 80 millitorrs, temperature are 0 ℃; Operating pressure in 5300 minutes～5500 minutes is that 5 millitorrs, temperature are 15 ℃.
CNB2007101214934A 2007-09-07 2007-09-07 Method for producing lithium ion battery anode material LiNi1-xCoxO2 Active CN100502107C (en)

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CN101475158B (en) * 2009-01-09 2011-05-25 北京工业大学 Preparation of lithium ionic cell anode material LiFeO4
CN103280550B (en) * 2013-05-28 2015-07-08 山东精工电子科技有限公司 Preparation method of lithium-iron button cell positive plate
CN107140696B (en) * 2017-05-25 2018-12-04 宁波工程学院 A kind of plasma fortified oxidizing roasting device for the nickelic positive electrode of synthesizing lithium ion battery
CN107204434B (en) * 2017-06-07 2020-04-17 安徽师范大学 Preparation method of three-dimensional flaky lithium cobaltate, lithium ion battery anode and lithium ion battery

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