CN103117386B - Method for determining manganese content of raw material manganese peroxide for synthesizing lithium manganese oxide spinel and raw material lithium carbonate/manganese peroxide ratio - Google Patents

Method for determining manganese content of raw material manganese peroxide for synthesizing lithium manganese oxide spinel and raw material lithium carbonate/manganese peroxide ratio Download PDF

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CN103117386B
CN103117386B CN201310046805.5A CN201310046805A CN103117386B CN 103117386 B CN103117386 B CN 103117386B CN 201310046805 A CN201310046805 A CN 201310046805A CN 103117386 B CN103117386 B CN 103117386B
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lithium
manganese dioxide
manganese
spinel
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刘爱强
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Liu Aiqiang
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Abstract

The invention relates to a method for determining manganese content of raw material manganese peroxide for synthesizing lithium manganese oxide spinel and raw material lithium carbonate/manganese peroxide ratio, which comprises the following steps: deducing the relational expression of product lithium/manganese mol ratio and manganese content of raw material manganese peroxide according to the chemical reaction equation; setting reference manganese content of manganese peroxide and lithium/manganese reference mol ratio of the synthetic product, and deducing the theoretically required reference amounts of lithium carbonate and manganese peroxide; synthesizing the lithium manganese oxide spinel according to the reference amounts of lithium carbonate and manganese peroxide under fitted technological conditions, measuring the lithium manganate lithium/manganese actual mol ratio by an ICP method, and acquiring the actual manganese content of the manganese peroxide; and by using the lithium carbonate as the reference amount, the manganese content of the manganese peroxide as the actual manganese content and the lithium/manganese ratio of the lithium manganate as the reference mol ratio, synthesizing the lithium manganese oxide spinel, and calculating the actually required amount of manganese peroxide. The method can avoid the process system errors caused by the technical process and the measuring system errors caused by the conventional chemical method, is simple and convenient, has the advantages of high accuracy and high practicality, and can implement continuous operation.

Description

The defining method of a kind of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content and oxide spinel lithium and manganese dioxide proportioning
Technical field
The invention belongs to technical field of lithium ion, be specifically related to the defining method of a kind of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content and oxide spinel lithium and manganese dioxide proportioning.
Background technology
Lithium ion battery have energy density high, have extended cycle life, the feature such as volume is little, lightweight, fail safe is good, be widely used in the power energy field such as the consumer electronic applications such as walkie electronic apparatus, digital camera, notebook computer and mobile communication and electric tool, electric bicycle, electric automobile.At present, the anode material for lithium-ion batteries that primary commercialization uses has: the lithium transition metal phosphate etc. of lithium manganate having spinel structure, layer structure lithium transition-metal oxide and olivine structural.Wherein spinel lithium manganate is due to the thermal stability of excellence, rich in natural resources characteristic and good fail safe, especially gets most of the attention.
The primary raw material of solid phase method industrialization synthetic spinel LiMn2O4 comprises the lithium carbonate as lithium source and the manganese dioxide as manganese source (electrolytic manganese dioxide and chemical manganese bioxide), and the oxide due to manganese exists multiple price, as Mn 2+, Mn 3+, Mn 4+deng, and each side reason such as impurity content difference, in raw material there is wave phenomenon in the Fe content of manganese oxide, directly has influence on the accuracy of pulp furnish and product elemental content.Therefore, before synthetic lithium manganate and batching, need accurately to determine the Fe content of raw material manganese dioxide and pulp furnish.
Traditional manganese dioxide manganese content test method, though be chemical analysis (as complexometry, titration etc.) or instrument test method (as ultraviolet spectrometer etc.), due to purity, the reason such as consumption or instrument and equipment operating accuracy of analytical reagent, all there is larger systematic error.
In the process of solid phase method industrialization synthetic spinel LiMn2O4, the Li/Mn mol ratio of synthetic product is the important parameter that sign pulp furnish precision and product elemental contain accuracy of measurement, is directly connected to the quality of LiMn2O4 product and the performance of lithium ion battery.The principal element affecting the Li/Mn mol ratio precision of synthetic product has:
(1) raw material ratio precision: systematic error as larger in the existence of raw material manganese dioxide manganese content test, the systematic error of the main assay of oxide spinel lithium all have influence on pulp furnish precision;
(2) building-up process process conditions: the systematic error that the technical process such as volatilization as the volatilization of impurity in building-up process, synthesis temperature, time, atmosphere, elemental lithium causes, also will be a greater impact to the precision of Li/Mn mol ratio.
In the prior art, owing to have ignored the procedures system error that synthesis process brings, there is larger measuring system error by mistake simultaneously, make the precision of the Li/Mn mol ratio of synthetic product and pulp furnish precision be difficult to accurately determine and control.
Summary of the invention
The object of the present invention is to provide the defining method of a kind of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content and oxide spinel lithium and manganese dioxide proportioning, by matching synthetic spinel LiMn2O4, the Li/Mn mol ratio of Accurate Measurement synthetic product realizes accurately determining raw material manganese dioxide Fe content and pulp furnish, thus realizes the accurate control to synthetic product Li/Mn mol ratio.This method avoid the procedures system error that technical process is brought, the measurement system error simultaneously conventional chemical processes measurement also can being avoided to bring, realize accurately determining to raw material manganese dioxide Fe content and pulp furnish under fit technique condition.
Above-mentioned purpose of the present invention is achieved by the following technical solution: the defining method of a kind of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content and oxide spinel lithium and manganese dioxide proportioning, containing following steps:
(1) take lithium carbonate as lithium source, take manganese dioxide as manganese source, synthetic spinel LiMn2O4, the quality of setting lithium carbonate is x, the quality of manganese dioxide is y, manganese dioxide Fe content is a (w.t.%), in the spinel lithium manganate of synthesis, the mol ratio of lithium/manganese is b, lithium carbonate and manganese dioxide carry out chemical reaction according to following chemical formula, according to the mol ratio of lithium carbonate and manganese dioxide, the relation formula between the mol ratio b drawing lithium/manganese in manganese dioxide Fe content a and spinel lithium manganate is: a × b=1.487 (xu%/y)
Wherein: u% is the mass percentage of oxide spinel lithium, wherein u% >=99.5%; As a rule, u% can reach 99.5% can meet raw materials requirement, but if the content of u% is higher, better, be usually set as constant;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2bmn 2o 4molecular weight, calculates depending on b value and obtains;
X is lithium carbonate quality;
Y is manganese dioxide quality;
Z generates product quality for reaction, is setting constant;
(2) the benchmark Fe content setting manganese dioxide is a 0(w.t.%), in spinel lithium manganate, the benchmark mol ratio of lithium/manganese is b 0, according to the chemical formula synthetic spinel LiMn2O4 in step (1), derive the benchmark consumption x of lithium carbonate required in theory 0, the benchmark consumption y of manganese dioxide 0, wherein x 0=(zb 0m 1)/(u%M 3), y 0=(2zM 2)/(a 0m 3);
(3) be x according to lithium carbonate quality 0, manganese dioxide quality is y 0, according to the chemical formula synthetic spinel LiMn2O4 in step (1), adopt ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate and measure for n time, and get its statistics average data will x 0and y 0, substitute into relational expression a × b=1.487 (xu%/y), draw the actual Fe content of manganese dioxide a ′ = ( 1.487 x 0 u % ) / ( y 0 b ′ ‾ ) ;
(4) lithium carbonate quality is kept to be x 0, the actual Fe content of manganese dioxide is a ', and in spinel lithium manganate, the mol ratio of lithium/manganese is b 0lithium carbonate and manganese dioxide are carried out chemical reaction according to the chemical formula in step (1), when generating spinel lithium manganate, according to relational expression a × b=1.487 (xu%/y), calculate the consumption y ' of the manganese dioxide of actual needs, y '=(1.487x 0u%)/(a ' × b 0); The actual amount proportioning of lithium carbonate and manganese dioxide is x 0: y '.
In step of the present invention (1)-(3), synthetic spinel LiMn2O4 carries out under fit technique condition.Namely the fit technique condition that the present invention is all is the actual building-up process of simulation spinel lithium manganate, when comprising laboratory lab scale, actual building-up process during simulation industrial production, also industrial condition during direct modeling spinel lithium manganate actual industrial production is comprised, adopt the process conditions adopted during the actual building-up process of simulation spinel lithium manganate, the impact of the factors such as procedures system error can be avoided.
Fit technique condition of the present invention is preferably the simulation process condition that there is not procedures system error with the actual building-up process of spinel lithium manganate.
Fit technique condition of the present invention is preferably the actual production synthetic technological condition of simulation spinel lithium manganate.
In step of the present invention (1) in manganese dioxide in Fe content a and spinel lithium manganate lithium/manganese mol ratio b between relation formula obtain in the following way: the mol ratio according to lithium carbonate and manganese dioxide: b:2=xu%/M 1: ya/M 2, draw a × b=(2u%M 2/ M 1) × (x/y), by u, M 1and M 2numerical value substitute into, obtain relational expression a × b=1.487 (x u%/y).
In step of the present invention (1), u% is the mass percentage of oxide spinel lithium, wherein u% >=99.5%; As a rule, u% can reach 99.5% can meet raw materials requirement, but if the content of u% is higher, better, be usually set as constant and accurately determining to raw material manganese dioxide Fe content and pulp furnish under fit technique condition of the present invention can not be affected.
The benchmark consumption x of lithium carbonate required in theory in step of the present invention (2) 0determining with magnitude relation by lithium carbonate and LiMn2O4, the benchmark consumption y of manganese dioxide required in theory in step (2) 0determining with magnitude relation by manganese dioxide and LiMn2O4.
In step of the present invention (2), the consumption of lithium carbonate, manganese dioxide is respectively benchmark consumption x 0, y 0time, the chemical equation of synthetic lithium manganate and the as follows with magnitude relation of each raw material:
Wherein: u% is the mass percentage of lithium carbonate, wherein u% >=99.5%; As a rule, u% can reach 99.5% can meet raw materials requirement, but if the content of u% is higher, better, be usually set as constant;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2b 0mn 2o 4molecular weight, depending on b 0value calculates and obtains;
X 0be the required in theory benchmark lithium carbonate quality of the spinel lithium manganate of z for generating quality;
Y 0be the required in theory benchmark manganese dioxide quality of the spinel lithium manganate of z for generating quality;
Z generates spinel lithium manganate quality for reaction, is setting constant.
The benchmark consumption x of lithium carbonate in the present invention 0refer under initial fit technique condition, when the benchmark Fe content adopting manganese dioxide is a 0(w.t.%), in spinel lithium manganate, the benchmark mol ratio of lithium/manganese is b 0, as needed preparation quality to be the spinel lithium manganate of z, then need the plan setting lithium carbonate and manganese dioxide to feed intake, wherein the plan of lithium carbonate feeds intake and is the benchmark consumption x of the lithium carbonate described in the application 0, the plan of manganese dioxide feeds intake and is the benchmark consumption y of the manganese dioxide described in the application 0.
57.4%≤a in step of the present invention (2) 0≤ 62%, 0.50≤b 0≤ 0.615.
Adopt ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate in step of the present invention (3) to measure for n time, obtain n survey calculation value b 1', b 2', b 3' ..., b ' n, then the arithmetic mean of n measured value , wherein n > 5.
Compared with prior art, tool of the present invention has the following advantages: the inventive method matching spinel lithium manganate technique building-up process, avoid the procedures system error that technical process is brought, the measurement system error simultaneously conventional chemical processes measurement also can being avoided to bring, realize accurately determining to raw material manganese dioxide Fe content and pulp furnish under fit technique condition, have simple, convenient, precision is high, practical and can the advantage of continued operation, is particularly useful for Industrialized Production Practice.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but the present invention is not limited in following examples, and following reagent is commercially available if no special instructions.
Embodiment 1
The synthetic spinel LiMn2O4 raw material manganese dioxide Fe content that the present embodiment provides and the defining method of oxide spinel lithium and manganese dioxide proportioning, containing following steps:
(1) the Fe content a (w.t.%) of raw material manganese dioxide and the relation formula of product LiMn2O4 lithium/manganese mol ratio b are derived: take lithium carbonate as lithium source, take manganese dioxide as manganese source, synthetic spinel LiMn2O4, wherein synthetic spinel LiMn2O4 carries out under fit technique condition, this fit technique condition is the process conditions that there is not procedures system error with the actual building-up process of spinel lithium manganate, the quality x of setting lithium carbonate, the quality of manganese dioxide is y, manganese dioxide Fe content is a, in the spinel lithium manganate of synthesis, the mol ratio of lithium/manganese is b, lithium carbonate and manganese dioxide carry out chemical reaction according to following chemical formula, by the mol ratio of lithium carbonate and manganese dioxide, relation formula between the mol ratio b drawing lithium/manganese in Fe content a and spinel lithium manganate in manganese dioxide is: a × b=1.487 (x u%/y)
Wherein: u% is the mass percentage of oxide spinel lithium, wherein u% >=99.5%, u%=99.5% is set;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2bmn 2o 4molecular weight, calculates depending on b value and obtains;
X is lithium carbonate quality;
Y is manganese dioxide quality;
Z generates product quality for reaction, is setting constant; Z for ease of calculating, all adopts 1000kg in the examples below, in fact, can be the quality of the spinel lithium manganate of any needs synthesis.
Wherein in manganese dioxide in Fe content a and spinel lithium manganate lithium/manganese mol ratio b between relation formula obtain in the following way: the mol ratio according to lithium carbonate and manganese dioxide: b:2=xu%/M 1: ya/M 2, draw a × b=(2u%M 2/ M 1) × (x/y), by u%, M 1and M 2numerical value substitute into, obtain relational expression a × b=1.48 (x/y).
(2) setting manganese dioxide benchmark Fe content is a 0(w.t.%), wherein a 0=0.59 (59w.t.%), in setting spinel lithium manganate, the benchmark mol ratio of lithium/manganese is b 0, wherein b 0=0.54, according to the chemical formula synthetic spinel LiMn2O4 in step (1), setting needs synthesis 1 ton of (z=1000kg) spinel lithium manganate, and its structural formula is Li 1.08mn 2o 4, derive the benchmark consumption x of lithium carbonate required in theory 0, the benchmark consumption y of manganese dioxide 0, the benchmark consumption x of lithium carbonate required in theory 0the benchmark consumption y of determining with magnitude relation by lithium carbonate and LiMn2O4, manganese dioxide required in theory 0being determining with magnitude relation by manganese dioxide and LiMn2O4, drawing x through deriving 0=(zb 0m 1)/(u%M 3), by b 0=0.54, M 1=73.89, M 3=181.368, u%=99.5% substitutes into x 0relational expression in, calculate x 0=221.10kg, y 0=(2zM 2)/(a 0m 3)=1026.81kg, by z=1000kg, M 2=54.938, a 0=0.59, M 3=181.368 substitute into y 0relational expression in, calculate y 0=1026.81kg;
(3) be x according to lithium carbonate quality 0=221.10kg, manganese dioxide quality are y 0=1026.81kg, according to the chemical formula synthetic spinel LiMn2O4 in step (1), adopts ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate and measures for 10 times, and get its statistics average data will x 0and y 0, substitute into relational expression a × b=1.48 (x/y), draw the actual Fe content of manganese dioxide a ′ = ( 1.48 x 0 ) / ( y 0 b ′ ‾ ) = 0.5970 ;
Wherein synthetic spinel LiMn2O4 carries out under actual process condition, and specific embodiment is:
A () takes the weight taking oxide spinel lithium and manganese dioxide respectively as pulp furnish according to benchmark proportioning, raw material granularity is respectively 4 ~ 6 μm, 18 ~ 20 μm;
B taken material is put into oblique type batch mixer by (), ratio of grinding media to material is 2:1 (weight), carries out ball mill mixing 6 hours;
C the material mixed is incubated 20 hours at 800 DEG C by (), carry out chemical reaction;
D the material that reacts completely after cooling, pulverizes and sieves and obtains the Li that granularity is 20 μm by () 1.08mn 2o 4powder.
Adopt ICP method measuring and calculating Li/Mn mol ratio:
Randomly draw 10 parts, synthetic product sample, ICP results of measuring is as shown in table (1):
Show the lithium/manganese ratio of each sample in (1) 10 part of spinel lithium manganate sample
(4) lithium carbonate quality is kept to be x 0, the actual Fe content of manganese dioxide is a ', and in spinel lithium manganate, the mol ratio of lithium/manganese is b 0, lithium carbonate and manganese dioxide are carried out chemical reaction according to the chemical formula in step (1), when generating spinel lithium manganate, according to relational expression a × b=1.48 (x/y), by x 0=221.10, a '=0.5970, b 0=0.54, calculate the consumption y ' of the manganese dioxide of actual needs, y '=(1.48x 0)/(a ' × b 0)=1015.03kg; The actual amount proportioning of lithium carbonate and manganese dioxide is x 0: y '=221.10:1015.03.
Embodiment 2
The synthetic spinel LiMn2O4 raw material manganese dioxide Fe content that the present embodiment provides and the defining method of oxide spinel lithium and manganese dioxide proportioning, containing following steps:
(1) the Fe content a (w.t.%) of raw material manganese dioxide and the relation formula of product LiMn2O4 lithium/manganese mol ratio b are derived: take lithium carbonate as lithium source, take manganese dioxide as manganese source, synthetic spinel LiMn2O4, wherein synthetic spinel LiMn2O4 carries out under fit technique condition, this fit technique condition is carry out under there are not the process conditions of procedures system error with the actual building-up process of spinel lithium manganate, the quality x of setting lithium carbonate, the quality of manganese dioxide is y, manganese dioxide Fe content is a, in the spinel lithium manganate of synthesis, the mol ratio of lithium/manganese is b, lithium carbonate and manganese dioxide carry out chemical reaction according to following chemical formula, according to the mol ratio of lithium carbonate and manganese dioxide, relation formula between the mol ratio b drawing lithium/manganese in Fe content a and spinel lithium manganate in manganese dioxide is: a × b=1.487 (x u%/y)
Wherein: u% is the mass percentage of oxide spinel lithium, wherein u% >=99.5%, u%=99.5% is set;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2bmn 2o 4molecular weight, calculates depending on b value and obtains;
X is lithium carbonate quality;
Y is manganese dioxide quality;
Z generates product quality for reaction, is setting constant;
Wherein in manganese dioxide in Fe content a and spinel lithium manganate lithium/manganese mol ratio b between relation formula obtain in the following way: the mol ratio according to lithium carbonate and manganese dioxide: b:2=xu%/M 1: ya/M 2, draw a × b=(2u%M 2/ M 1) × (x/y), by u%, M 1and M 2numerical value substitute into, obtain relational expression a × b=1.48 (x/y).
(2) setting benchmark Fe content is a 0(w.t.%), wherein a 0=0.574 (57.4w.t.%), in setting spinel lithium manganate, the benchmark mol ratio of lithium/manganese is b 0, wherein b 0=0.615, according to the chemical formula synthetic spinel LiMn2O4 in step (1), setting needs synthesis 1 ton of (z=1000kg) spinel lithium manganate, and its structural formula is Li 1.23mn 2o 4, derive the benchmark consumption x of lithium carbonate required in theory 0, the benchmark consumption y of manganese dioxide 0, the benchmark consumption x of lithium carbonate required in theory 0the benchmark consumption y of determining with magnitude relation by lithium carbonate and LiMn2O4, manganese dioxide required in theory 0being determining with magnitude relation by manganese dioxide and LiMn2O4, drawing x through deriving 0=(zb 0m 1)/(u%M 3), by b 0=0.615, M 1=73.89, M 3=182.409, u%=99.5% substitutes into x 0relational expression in, calculate x 0=250.38kg, y 0=(2zM 2)/(a 0m 3)=1049.41kg, by z=1000kg, M 2=54.938, a 0=0.574, M 3=182.409 substitute into y 0relational expression in, calculate y 0=1049.41kg;
(3) be x according to lithium carbonate quality 0=250.38kg, manganese dioxide quality are y 0=1049.41kg, according to the chemical formula synthetic spinel LiMn2O4 in step (1), adopts ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate and measures for 10 times, and get its statistics average data will , x 0and y 0, substitute into relational expression a × b=1.48 (x/y), draw the actual Fe content of manganese dioxide a ′ = ( 1.487 x 0 u % ) / ( y 0 b ′ ‾ ) = 0.5884 ;
Wherein synthetic spinel LiMn2O4 carries out under actual process condition, is only herein and enumerates, and concrete technology condition can with reference to the preparation process of each spinel lithium manganate, and specific embodiment is:
A () takes the weight of oxide spinel lithium and manganese dioxide as pulp furnish according to benchmark proportioning, raw material granularity is respectively 4 ~ 6 μm, 18 ~ 20 μm;
B taken material is put into oblique type batch mixer by (), ratio of grinding media to material is 2:1 (weight), carries out ball mill mixing 6 hours;
C the material mixed is incubated 20 hours at 800 DEG C by (), carry out chemical reaction;
D the material that reacts completely after cooling, pulverizes and sieves and obtains the Li that granularity is 20 μm by () 1.23mn 2o 4powder.
Adopt ICP method measuring and calculating Li/Mn mol ratio:
Randomly draw 10 parts, synthetic product sample, ICP results of measuring is as shown in table (2):
Show the lithium/manganese ratio of each sample in (2) 10 parts of spinel lithium manganate samples
(4) lithium carbonate quality is kept to be x 0, the actual Fe content of manganese dioxide is a ', and in spinel lithium manganate, the mol ratio of lithium/manganese is b 0, lithium carbonate and manganese dioxide are carried out chemical reaction according to the chemical formula in step (1), when generating spinel lithium manganate, according to relational expression a × b=1.48 (x/y), by x 0=250.38, a '=0.5884, b 0=0.615, calculate the consumption y ' of the manganese dioxide of actual needs, y '=(1.487x 0u%)/(a ' × b 0)=1024.03kg; The actual amount proportioning of lithium carbonate and manganese dioxide is x 0: y '=250.38:1024.03.
Embodiment 3
The synthetic spinel LiMn2O4 raw material manganese dioxide Fe content that the present embodiment provides and the defining method of oxide spinel lithium and manganese dioxide proportioning, containing following steps:
(1) the Fe content a (w.t.%) of raw material manganese dioxide and the relation formula of product LiMn2O4 lithium/manganese mol ratio b are derived: take lithium carbonate as lithium source, take manganese dioxide as manganese source, synthetic spinel LiMn2O4, wherein synthetic spinel LiMn2O4 carries out under fit technique condition, this fit technique condition is carry out under there are not the process conditions of procedures system error with the actual building-up process of spinel lithium manganate, the quality x of setting lithium carbonate, the quality of manganese dioxide is y, manganese dioxide Fe content is a, in the spinel lithium manganate of synthesis, the mol ratio of lithium/manganese is b, lithium carbonate and manganese dioxide carry out chemical reaction according to following chemical formula, according to the mol ratio of lithium carbonate and manganese dioxide, relation formula between the mol ratio b drawing lithium/manganese in Fe content a and spinel lithium manganate in manganese dioxide is: a × b=1.487 (x u%/y)
Wherein: u% is the mass percentage of oxide spinel lithium, wherein u% >=99.5%, u%=99.5% is set;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2bmn 2o 4molecular weight, calculates depending on b value and obtains;
X is lithium carbonate quality;
Y is manganese dioxide quality;
Z generates product quality for reaction, is setting constant;
Wherein in manganese dioxide in Fe content and spinel lithium manganate lithium/manganese mol ratio b between relation formula obtain in the following way: the mol ratio according to lithium carbonate and manganese dioxide: b:2=xu%/M 1: ya/M 2, draw a × b=(2u%M 2/ M 1) × (x/y), by u%, M 1and M 2numerical value substitute into, obtain relational expression a × b=1.48 (x/y).
(2) setting benchmark Fe content is a 0(w.t.%), wherein a 0=0.62 (62w.t.%), in setting spinel lithium manganate, the benchmark mol ratio of lithium/manganese is b 0, wherein b 0=0.50, according to the chemical formula synthetic spinel LiMn2O4 in step (1), setting needs synthesis 1 ton of (z=1000kg) spinel lithium manganate, and its structural formula is Li 1.00mn 2o 4, derive the benchmark consumption x of lithium carbonate required in theory 0, the benchmark consumption y of manganese dioxide 0, the benchmark consumption x of lithium carbonate required in theory 0the benchmark consumption y of determining with magnitude relation by potash and LiMn2O4, manganese dioxide required in theory 0being determining with magnitude relation by manganese dioxide and LiMn2O4, drawing x through deriving 0=(zb 0m 1)/(u%M 3), by b 0=0.50, M 1=73.89, M 3=180.813, u%=99.5% substitutes into x 0relational expression in, calculate x 0=205.35kg, y 0=(2zM 2)/(a 0m 3)=980.13kg, by z=1000kg, M 2=54.938, a 0=0.50, M 3=180.813 substitute into y 0relational expression in, calculate y 0=980.13kg;
(3) be x according to lithium carbonate quality 0=205.35kg, manganese dioxide quality are y 0=980.13kg, according to the chemical formula synthetic spinel LiMn2O4 in step (1), adopts ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate and measures for 10 times, and get its statistics average data will x 0and y 0, substitute into relational expression a × b=1.48 (x/y), draw the actual Fe content of manganese dioxide a ′ = ( 1.48 x 0 ) / ( y 0 b ′ ‾ ) = 0.5992 ;
Wherein synthetic spinel LiMn2O4 carries out under actual process condition, and specific embodiment is:
A () takes the weight of oxide spinel lithium and manganese dioxide as pulp furnish according to benchmark proportioning, raw material granularity is respectively 4 ~ 6 μm, 18 ~ 20 μm;
B taken material is put into oblique type batch mixer by (), ratio of grinding media to material is 2:1 (weight), carries out ball mill mixing 6 hours;
C the material mixed is incubated 16 hours at 780 DEG C by (), carry out chemical reaction;
D the material that reacts completely after cooling, pulverizes and sieves and obtains the Li that granularity is 20 μm by () 1.00mn 2o 4powder.
Adopt ICP method measuring and calculating Li/Mn mol ratio:
Randomly draw 10 parts, synthetic product sample, ICP results of measuring is as shown in table (3):
Show the lithium/manganese ratio of each sample in (3) 10 parts of spinel lithium manganate samples
(4) lithium carbonate quality is kept to be x 0, the actual Fe content of manganese dioxide is a ', and in spinel lithium manganate, the mol ratio of lithium/manganese is b 0, lithium carbonate and manganese dioxide are carried out chemical reaction according to the chemical formula in step (1), when generating spinel lithium manganate, according to relational expression a × b=1.48 (x/y), by x 0=205.35, a '=0.5992, b 0=0.50, calculate the consumption y ' of the manganese dioxide of actual needs, y '=(1.48x 0)/(a ' × b 0)=1014.41kg; The actual amount proportioning of lithium carbonate and manganese dioxide is x 0: y '=205.35:1014.41.
Embodiment 4
The synthetic spinel LiMn2O4 raw material manganese dioxide Fe content that the present embodiment provides and the defining method of oxide spinel lithium and manganese dioxide proportioning, containing following steps:
(1) the Fe content a (w.t.%) of raw material manganese dioxide and the relation formula of product LiMn2O4 lithium/manganese mol ratio b are derived: take lithium carbonate as lithium source, take manganese dioxide as manganese source, synthetic spinel LiMn2O4, wherein synthetic spinel LiMn2O4 carries out under fit technique condition, this fit technique condition is the process conditions that there is not procedures system error with the actual building-up process of spinel lithium manganate, the quality x of setting lithium carbonate, the quality of manganese dioxide is y, manganese dioxide Fe content is a, in the spinel lithium manganate of synthesis, the mol ratio of lithium/manganese is b, lithium carbonate and manganese dioxide carry out chemical reaction according to following chemical formula, by the mol ratio of lithium carbonate and manganese dioxide, relation formula between the mol ratio b drawing lithium/manganese in manganese dioxide Fe content a and spinel lithium manganate is: a × b=1.487 (x u%/y)
Wherein: u% is the mass percentage of oxide spinel lithium, wherein u% >=99.5%, u%=99.5% is set;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2bmn 2o 4molecular weight, calculates depending on b value and obtains;
X is lithium carbonate quality;
Y is manganese dioxide quality;
Z generates product quality for reaction, is setting constant;
Wherein in manganese dioxide in Fe content a and spinel lithium manganate lithium/manganese mol ratio b between relation formula obtain in the following way: the mol ratio according to lithium carbonate and manganese dioxide: b:2=xu%/M 1: ya/M 2, draw a × b=(2u%M 2/ M 1) × (x/y), by u%, M 1and M 2numerical value substitute into, obtain relational expression a × b=1.48 (x/y).
(2) setting manganese dioxide benchmark Fe content is a 0(w.t.%), wherein a 0=0.60 (60w.t.%), in setting spinel lithium manganate, the benchmark mol ratio of lithium/manganese is b 0, wherein b 0=0.56, according to the chemical formula synthetic spinel LiMn2O4 in step (1), setting needs synthesis 1 ton of (z=1000kg) spinel lithium manganate, and its structural formula is Li 1.12mn 2o 4, derive the benchmark consumption x of lithium carbonate required in theory 0, the benchmark consumption y of manganese dioxide 0, the benchmark consumption x of lithium carbonate required in theory 0the benchmark consumption y of determining with magnitude relation by lithium carbonate and LiMn2O4, manganese dioxide required in theory 0being determining with magnitude relation by manganese dioxide and LiMn2O4, drawing x through deriving 0=(zb 0m 1)/(u%M 3), by b 0=0.54, M 1=73.89, M 3=181.646, u%=99.5% substitutes into x 0relational expression in, calculate x 0=228.94kg, y 0=(2zM 2)/(a 0m 3)=1008.15kg, by z=1000kg, M 2=54.938, a 0=0.59, M 3=181.646 substitute into y 0relational expression in, calculate y 0=1008.15kg;
(3) be x according to lithium carbonate quality 0=228.94kg, manganese dioxide quality are y 0=1008.15kg, according to the chemical formula synthetic spinel LiMn2O4 in step (1), adopts ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate and measures for 8 times, and get its statistics average data will x 0and y 0, substitute into relational expression a × b=1.48 (x/y), draw the actual Fe content of manganese dioxide a ′ = ( 1.48 x 0 ) / ( y 0 b ′ ‾ ) = 0.5958 ;
Wherein synthetic spinel LiMn2O4 carries out under actual process condition, and specific embodiment is:
A () takes the weight taking oxide spinel lithium and manganese dioxide respectively as pulp furnish according to benchmark proportioning, raw material granularity is respectively 4 ~ 6 μm, 18 ~ 20 μm;
B taken material is put into oblique type batch mixer by (), ratio of grinding media to material is 2:1 (weight), carries out ball mill mixing 6 hours;
C the material mixed is incubated 20 hours at 800 DEG C by (), carry out chemical reaction;
D the material that reacts completely after cooling, pulverizes and sieves and obtains the Li that granularity is 20 μm by () 1.12mn 2o 4powder.
Adopt ICP method measuring and calculating Li/Mn mol ratio:
Randomly draw 8 parts, synthetic product sample, ICP results of measuring is as shown in table (4):
Show the lithium/manganese ratio of each sample in (4) 8 parts of spinel lithium manganate samples
(4) lithium carbonate quality is kept to be x 0, the actual Fe content of manganese dioxide is a ', and in spinel lithium manganate, the mol ratio of lithium/manganese is b 0, lithium carbonate and manganese dioxide are carried out chemical reaction according to the chemical formula in step (1), when generating spinel lithium manganate, according to relational expression a × b=1.48 (x/y), by x 0=228.94, a '=0.5958, b 0=0.56, calculate the consumption y ' of the manganese dioxide of actual needs, y '=(1.48x 0)/(a ' × b 0)=1015.53kg; The actual amount proportioning of lithium carbonate and manganese dioxide is x 0: y '=228.94:1015.53.
Embodiment 5
The synthetic spinel LiMn2O4 raw material manganese dioxide Fe content that the present embodiment provides and the defining method of oxide spinel lithium and manganese dioxide proportioning, containing following steps:
(1) the Fe content a (w.t.%) of raw material manganese dioxide and the relation formula of product LiMn2O4 lithium/manganese mol ratio b are derived: take lithium carbonate as lithium source, take manganese dioxide as manganese source, synthetic spinel LiMn2O4, wherein synthetic spinel LiMn2O4 carries out under fit technique condition, this fit technique condition is the process conditions that there is not procedures system error with the actual building-up process of spinel lithium manganate, the quality x of setting lithium carbonate, the quality of manganese dioxide is y, in manganese dioxide, Fe content is a, in the spinel lithium manganate of synthesis, the mol ratio of lithium/manganese is b, lithium carbonate and manganese dioxide carry out chemical reaction according to following chemical formula, by the mol ratio of lithium carbonate and manganese dioxide, relation formula between the mol ratio b drawing lithium/manganese in manganese dioxide Fe content a and spinel lithium manganate is: a × b=1.487 (x u%/y)
Wherein: u% is the mass percentage of oxide spinel lithium, wherein u% >=99.5%, u%=99.98% is set;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2bmn 2o 4molecular weight, calculates depending on b value and obtains;
X is lithium carbonate quality;
Y is manganese dioxide quality;
Z generates product quality for reaction, is setting constant;
Wherein in manganese dioxide in Fe content a and spinel lithium manganate lithium/manganese mol ratio b between relation formula obtain in the following way: the mol ratio according to lithium carbonate and manganese dioxide: b:2=xu%/M 1: ya/M 2, draw a × b=(2u%M 2/ M 1) × (x/y), by u%, M 1and M 2numerical value substitute into, obtain relational expression a × b=1.487 (x/y).
(2) setting manganese dioxide benchmark Fe content is a 0(w.t.%), wherein a 0=0.595 (59.5w.t.%), in setting spinel lithium manganate, the benchmark mol ratio of lithium/manganese is b 0, wherein b 0=0.58, according to the chemical formula synthetic spinel LiMn2O4 in step (1), setting needs synthesis 1 ton of (z=1000kg) spinel lithium manganate, and its structural formula is Li 1.16mn 2o 4, derive the benchmark consumption x of lithium carbonate required in theory 0, the benchmark consumption y of manganese dioxide 0, the benchmark consumption x of lithium carbonate required in theory 0the benchmark consumption y of determining with magnitude relation by lithium carbonate and LiMn2O4, manganese dioxide required in theory 0being determining with magnitude relation by manganese dioxide and LiMn2O4, drawing x through deriving 0=(zb 0m 1)/(u%M 3), by b 0=0.58, M 1=73.89, M 3=181.924, u%=99.98% substitutes into x 0relational expression in, calculate x 0=235.62kg, y 0=(2zM 2)/(a 0m 3)=1015.07kg, by z=1000kg, M 2=54.938, a 0=0.59, M 3=181.924 substitute into y 0relational expression in, calculate y 0=1015.07kg;
(3) be x according to lithium carbonate quality 0=235.62kg, manganese dioxide quality are y 0=1015.07kg, according to the chemical formula synthetic spinel LiMn2O4 in step (1), adopts ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate and measures for 10 times, and get its statistics average data will x 0and y 0, substitute into relational expression a × b=1.487 (x/y), draw the actual Fe content of manganese dioxide a ′ = ( 1.487 x 0 ) / ( y 0 b ′ ‾ ) = 0.5964 ;
Wherein synthetic spinel LiMn2O4 carries out under actual process condition, and specific embodiment is:
A () takes the weight taking oxide spinel lithium and manganese dioxide respectively as pulp furnish according to benchmark proportioning, raw material granularity is respectively 4 ~ 6 μm, 18 ~ 20 μm;
B taken material is put into oblique type batch mixer by (), ratio of grinding media to material is 2:1 (weight), carries out ball mill mixing 6 hours;
C the material mixed is incubated 20 hours at 800 DEG C by (), carry out chemical reaction;
D the material that reacts completely after cooling, pulverizes and sieves and obtains the Li that granularity is 20 μm by () 1.16mn 2o 4powder.
Adopt ICP method measuring and calculating Li/Mn mol ratio:
Randomly draw 10 parts, synthetic product sample, ICP results of measuring is as shown in table (5):
Show the lithium/manganese ratio of each sample in (5) 10 parts of spinel lithium manganate samples
(4) lithium carbonate quality is kept to be x 0, the actual Fe content of manganese dioxide is a ', and in spinel lithium manganate, the mol ratio of lithium/manganese is b 0, lithium carbonate and manganese dioxide are carried out chemical reaction according to the chemical formula in step (1), when generating spinel lithium manganate, according to relational expression a × b=1.48 (x/y), by x 0=235.62, a '=0.5964, b 0=0.58, calculate the consumption y ' of the manganese dioxide of actual needs, y '=(1.487x 0)/(a ' × b 0)=1012.87kg; The actual amount proportioning of lithium carbonate and manganese dioxide is x 0: y '=235.62:1012.87.
The specific embodiment more than enumerated is the explanation carried out the present invention.It is pointed out that above embodiment is only for the invention will be further described, do not form limiting the scope of the invention, the nonessential amendment that other people prompting according to the present invention is made and adjustment, still belong to protection scope of the present invention.

Claims (9)

1. a defining method for synthetic spinel LiMn2O4 raw material manganese dioxide Fe content and oxide spinel lithium and manganese dioxide proportioning, is characterized in that comprising following steps:
(1) take lithium carbonate as lithium source, take manganese dioxide as manganese source, synthetic spinel LiMn2O4, the quality of setting lithium carbonate is x, the quality of manganese dioxide is y, manganese dioxide Fe content is a (w.t.%), in the spinel lithium manganate of synthesis, the mol ratio of lithium/manganese is b, lithium carbonate and manganese dioxide carry out chemical reaction according to following chemical formula, according to the mol ratio of lithium carbonate and manganese dioxide, the relation formula between the mol ratio b drawing lithium/manganese in manganese dioxide Fe content a and spinel lithium manganate is: a × b=1.487 (xu%/y)
Wherein: u% is the mass percentage of oxide spinel lithium, wherein u% >=99.5%;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2bmn 2o 4molecular weight, calculates depending on b value and obtains;
X is lithium carbonate quality;
Y is manganese dioxide quality;
Z generates product quality for reaction, is setting constant;
(2) the benchmark Fe content setting manganese dioxide is a 0(w.t.%), in spinel lithium manganate, the benchmark mol ratio of lithium/manganese is b 0, according to the chemical formula synthetic spinel LiMn2O4 in step (1), derive the benchmark consumption x of lithium carbonate required in theory 0, the benchmark consumption y of manganese dioxide 0, wherein x 0=(zb 0m 1)/(u%M 3), y 0=(2zM 2)/(a 0m 3);
(3) be x according to lithium carbonate quality 0, manganese dioxide quality is y 0, according to the chemical formula synthetic spinel LiMn2O4 in step (1), adopt ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate and measure for n time, and get its statistics average data will x 0and y 0, substitute into relational expression a × b=1.487 (xu%/y), draw the actual Fe content of manganese dioxide a ′ = ( 1.487 x 0 u % ) / ( y 0 b ′ ‾ ) ;
(4) lithium carbonate quality is kept to be x 0, the actual Fe content of manganese dioxide is a ', and in spinel lithium manganate, the mol ratio of lithium/manganese is b 0lithium carbonate and manganese dioxide are carried out chemical reaction according to the chemical formula in step (1), when generating spinel lithium manganate, according to relational expression a × b=1.487 (xu%/y), calculate the consumption y ' of the manganese dioxide of actual needs, y '=(1.487x 0u%)/(a ' × b 0); The actual amount proportioning of lithium carbonate and manganese dioxide is x 0: y '.
2. the defining method of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content according to claim 1 and oxide spinel lithium and manganese dioxide proportioning, is characterized in that: in step (1)-(3), synthetic spinel LiMn2O4 carries out under fit technique condition.
3. the defining method of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content according to claim 2 and oxide spinel lithium and manganese dioxide proportioning, is characterized in that: described fit technique condition is the simulation process condition that there is not procedures system error with the actual building-up process of spinel lithium manganate.
4. the defining method of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content according to claim 2 and oxide spinel lithium and manganese dioxide proportioning, is characterized in that: described fit technique condition is the actual production synthetic technological condition of simulation spinel lithium manganate.
5. the defining method of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content according to claim 1 and oxide spinel lithium and manganese dioxide proportioning, is characterized in that: in step (1) in manganese dioxide in Fe content a and spinel lithium manganate lithium/manganese mol ratio b between relation formula obtain in the following way: the mol ratio according to lithium carbonate and manganese dioxide: b:2=xu%/M 1: ya/M 2, draw a × b=(2u%M 2/ M 1) × (x/y), by u, M 1and M 2numerical value substitute into, obtain relational expression a × b=1.487 (xu%/y).
6. the defining method of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content according to claim 1 and oxide spinel lithium and manganese dioxide proportioning, is characterized in that: the benchmark consumption x of lithium carbonate required in theory in step (2) 0determining with magnitude relation by lithium carbonate and LiMn2O4, the benchmark consumption y of manganese dioxide required in theory in step (2) 0determining with magnitude relation by manganese dioxide and LiMn2O4.
7. the defining method of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content according to claim 1 and oxide spinel lithium and manganese dioxide proportioning, is characterized in that: in step (2), the consumption of lithium carbonate, manganese dioxide is respectively benchmark consumption x 0, y 0time, the chemical equation of synthetic lithium manganate and the as follows with magnitude relation of each raw material:
Wherein: u% is the mass percentage of lithium carbonate, wherein u% >=99.5%;
M 1for Li 2cO 3molecular weight is 73.89;
M 2for the atomic weight of Mn, be 54.938;
M 3for Li 2b 0mn 2o 4molecular weight, depending on b 0value calculates and obtains;
X 0be the required in theory benchmark lithium carbonate quality of the spinel lithium manganate of z for generating quality;
Y 0be the required in theory benchmark manganese dioxide quality of the spinel lithium manganate of z for generating quality;
Z generates spinel lithium manganate quality for reaction, is setting constant.
8. the defining method of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content according to claim 1 and oxide spinel lithium and manganese dioxide proportioning, is characterized in that: 57.4%≤a in step (2) 0≤ 62%, 0.50≤b 0≤ 0.615.
9. the defining method of synthetic spinel LiMn2O4 raw material manganese dioxide Fe content according to claim 1 and oxide spinel lithium and manganese dioxide proportioning, it is characterized in that: adopt ICP method to carry out equally accurate to the actual mol ratio of lithium/manganese in spinel lithium manganate in step (3) and measure for n time, obtain n survey calculation value b 1', b 2', b 3' ..., b ' n, then the arithmetic mean of n measured value wherein n > 5.
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