CA1134595A - Mno.sub.2 derived from limn.sub.2o.sub.4 - Google Patents

Mno.sub.2 derived from limn.sub.2o.sub.4

Info

Publication number
CA1134595A
CA1134595A CA000335495A CA335495A CA1134595A CA 1134595 A CA1134595 A CA 1134595A CA 000335495 A CA000335495 A CA 000335495A CA 335495 A CA335495 A CA 335495A CA 1134595 A CA1134595 A CA 1134595A
Authority
CA
Canada
Prior art keywords
acid
manganese dioxide
ray diffraction
electrolyte
electrochemical cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000335495A
Other languages
French (fr)
Inventor
James C. Hunter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Application granted granted Critical
Publication of CA1134595A publication Critical patent/CA1134595A/en
Expired legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Saccharide Compounds (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE
A new form of manganese dioxide having an x-ray diffraction pattern resembling none of the x-ray patterns of the known forms of manganese dioxide is manufactured by acid treatment of LiMo2O4.

Description

3~i95 113~8 This invention relates to a new form of manganese dioxide and a method for preparing the ~3me. In par~icular this invention relates ~o a new :Eoxm of manganese dioxide hav~ng an ~-ray diffraction pattern :
not hereto~oreexhibited by ~ny previowsly known forms of manganese diox~de.
This invention provides a novel form of mar~ganese dioxide which is made by acid treatment of the known ~ :
material LiMn204.
Manganese dloxide (~nO2~ is a well-kno~ substance commonly used in electrochemical cells, such as d~y cell batteries, as an active cathode material. Manganese dioxide has been known to exist in various crystalline forms among which pyrolusite and ~sutite are commonly found in nature. Ramsdellite is also found in nature~
bu~ to a lesser extent. Other forms of manganese d~oxide are ~nown, ei~her naturally oc~urring or man-made3 but none of these alone or ~n combina :ion has the x-ray diffracticn pa~tern of the manganese dioxide of ~his invention.
L~Mn204, a sp~nel, is reported by WicWham and Crof~
~D. G. Wickh~m & WO J. Crof~, IL,~59~L_~ZIa~e~ 3 7 351 (1958) to form whenever lithium carbonate and any ox;d~ of slanganese are ~aken in a 2:1 molar ra~io of ~/Li, and heated at 800~90û~C ln a~r. The product ~2 3 ~ 5 1~38~

L~Mn204 ( a blue colored materi~l~ contain~ equal amo~n~s of Mn(III~ ~nd Mn(IV), and accord~ngly has a manganese peroxidation value of 75% ~% peroxidation i~ defined as ~he degree to ~hlch the manganese oxidation æta~e has been raised from Mn(II) to Mn(IV). Thus, MnO has 0~/0 peroxidation and MnO~ has 100% peroxidation3. Wlc~ham and Croft also reported that using excess Li in the reaction led to formation of a mixture o~ LiMn2q~and ~12~nO3 l~a red material~, while excess Mn led to a mîxture containillg Mn203 in addition ~ the LiMn2 ~ . It should be noted that other preparative teehniques are possible for prepar-ing LiMn204, in addition to those described by Wickham ~nd Croft~ Other lithium or manganese c~mpounds can be used as starting ma~erials provided they dec~mpose to lithium or manganese oxides under the reaction condlt~ons used.
The novel m~nganese dioxide of th~s invention is made by acld treatment of LiM~2Q4. The product of the acid trea~ment is a substantially pure MnO2 whose x-ray pattern is ~ear~y iden~ical to that of the starting material LiMh20~, a spinel. The x-ray pattern of the MnO~ of this invention differs from that of LiMn204 in that there ls a slight shift in peak positions, ~ndicating a lattlce contraction upon formation of the novel form of m~nganese dioxide~ which we sha~l refer to ~eLnafter as ', 31 39L~5 "J~2"- The 71,~ designation, to the best of our knowledge, has not been used ~n the art to designate a form of ~nO2 Thus, while LiMn20~ is a cublc spirlel with aD~ 8~24 A..~02 appears ~o have a closely related O O
structure with a~ 8.07 A + n.o2 A. Th~ teD "a~," as used herein is the well~lcno~ ter~n used in cryst~llograph~
whichrefers to the edge di~nension of the cub~c unit cell.
A raIlge of compositions intermediate between Li~n204 and ~ :
~MnO~ can be produced by controllirlg the acid treatiT)g conditions, and such composi~ions can be represented by the empirical fonnula Li~204 where O~x<1, and have x-ray patterns with charac~ristics of both Li~n20~ andl~
~2 X-ray diffraction ~s a well-knowrl and relia~le test method for the determ~nation of the structure of crystalsO
~hen a crystall~e struc~ure is bombarded ~ith ~rays, some of the x-rays are scattered and changes in the phase relations betwe~3n the rays scattered by diffexent atoms in ~he crystal result in a diffraction pattexn character-istic of the spatial arrangement of the a~oms in the crystal. The positions of the diLffraction lines in a typic:al x-ray pattern ara oi~ten referred to as d-values, indicated in Angstroms `(A~, and correspond to the plane spacings in the bo~arded cry~tal. These pl~ne spacirlg --4~

3~ 5 and the relative ~ntensities of the lines are charactex istic of the structure of . given crystal .
Identifi~ation of a substance by its x-ray dlffract~on pattern may be achieved by direet eomparison w~ch the patterns of known substanees, whlch is made easier through the use o~ published x-ray pa~terns rlassified in the card index o~ ~he American Society for Testing and Mat erial s (ASTM) .
~or the determialat:i Oll of the x-ray pattenns o the materials deseribed herein conventional powder diffraction ~echniques were used. The rad~ation was Fe K~C, or C:u K~:, and a oonventional scintillation counter detector was used, with the resul ting peaks displayed on a strlp chart recorder. d-values for the difraction lines were calcul~ted from the line positIorls and the wavelength of the impinging radiation, using standard tables.
The ideal starting material for preparingl-~02 is Li~2t)4, which has a ~ peroxidation v~lue of 75%.
However3 in practice, i'c has keen ~o~d that sa~isfact:ory results are obtained over a range of Mn peroxidation values, where the Mn/Li ratio ~n the starking mlxtur~
used to form L~ID~O4 varies somewhat from the ideal 2:1.
As explained by Wickham and Croft, for ~$n/Li of less than
2 :1 (i. e . e~cess Li) some Li2~O3 forms . This is a i,3 4 5~ ~ -113~8 distinctively red mater~al~ containlng Mn(IV~. It is not affected by acid tre~tment, and it is of very low electroeh~m~cal activity. Even a~ a 2:1 Mn/Li ratio s~me of this material 1s often seen, proba~ly due ~o incsmplete reaction o form L~Mn20~, because of localized var~ations of the MnlLi rakio in the startlng m~xture.
The use of a slight (up to 10~) exeess Mn ~n the ini~ial mixture used to form L~Mn20~ tends to prevent formation of Li2MnO3 and ult~mately results in ~-MhO2 of good actiYity. Thus, the optimum material for forming ~ -~nO2 ~s a L~Mn20~ prepared in such a way as to be free of Li2MnO3, and ~here some exc~ss Mn203 can be tolerated;
~ where the peroxidatio~ is in the range of 70-75~ ~
In accordance wi~h the present invention ~here is provided a new crystalline form of mEnganeSe dioxide with an x-ray diffraction pattexn havi~g d-values of 4.~4A, O O O ~, O O O
2.42A, 2.31A~ 2.olA~ 1.84A, 1.55A and 1.42A, ~ 0.02A in . each instance.
In acc~rance with the present inv~t~on t~e is also pro~ided a method for produci~g the m~nganese dioxide of this inven~ion ~Jhich enc~mpasses ac~d-trea~ing ~Mn204 under condi~ions speclfied in more detail hereinafter.
The trea~ment procedure ~ypically involves suspending L ~ 04 in water at ro~m temperature by stirrin~ and ~hen adding acid while con~inuing to stir~

45~

~nd while m~ni.toring the pH of the olutlon phase, For satisfactory conversion, on ~che order of greater than aboslt 90% o the I,i~h2O4 to ~heA-~o2 of this $nvention9 ac~ d treatment should continue until the p~l of the solution phase stabili~es ~ below about pH 2.5, preferably below about 2. If a manganese oxide Ore cont:aining large amounts of impurities is used as a starting material to make the I,i~204, then a more severe acid treatment, (l.e., stronger aeid ar.d/or higher temperature) may be requi:red to r~move the acid-solu~le impurities while achieving ~he desired conversion to 'che,)~-MnO~.
The acids which are suitable for ~reating Li~n20b in the practice o this invention include, but are not l~mited to acids such as H2S04 ~ HCl, or HNO3; other suitable acids selected by those skilled in the art may be employed.
The acids may be used in dilute conc~ntrations generally on ', the order of about ~ to about 10 normality.
The manganese diox:Ede of ~his invention is sui~able for use in a number of applications where manganese dioxide has been employed in the past. The most extensive use of manganese dioxide has ~een in electrochemical cel1s, in par~icular in dry cell bat~eries, which typically comprise a maQganese d~oxide cathode, a zinc anode, and an aqueous elee~roly~e (such as aqueous N~4Cl and ZnCl~

fiolu~ions)~ While the most widely u~ed electro:Lytes in dry cell~ have been in aclueous fo~, the manganese dioxide of this invention is ~3specia1 ly u~eful with non-aqueous e~ ectrolytes 9 such as tho~e comprislng organic solutions of light metal salt~; such as LiBF~, in propylene carbonate-dimethoxyethane ~ or LiAsF6 in methylformal:e propylene carbonate, and should also be useful with solid electrolytes such as li'chium-subs~citu~ed beta-alumina .
In the drawing:
Fig. ~: is a graph showing discharge behavior of MnO2 in comparison with that of heat treated EM9 in a non-aqueous el~ctrolyte as explained more fully in Example IV hereinafter.
The ~ollowing examples are set forth as being merely illustrative of the invention and are not inte~ded i~ a~y =an~er to be limitative thereof. Unless otherwise indieated, all parts an:d percentages are by we~ght, ' ' This example illu~trates the preparation of~ -MnO2.
20 ~s of R -~2 ~rea~ent grade pyrolustie) were ground together with 4~25 gms of Li2C03~ heated in a1r to 835~C for 10 minutes, cooled, and then reheated to 850C
in air for or~e hour 9 and cooled to room t~mperature . The resul~ing reactio~ product was a lblue powder found ~o b~
:`:
3 ~9 5 113~8 subs~antially p~re L~Mn204. About 15 gms of this reactlon product w~re pla~ed in a beaker, a~out 400 mls wa~er added, and while s~irring, 15% H2S04 was ~lowly added until the solution phase pH stabiliæed at 2. After allowing solid material to set~le the supernatant liquid was decanted and the remainlng solid was washed by decantation until the wash solutions were neutral~ The solid was ~hen collected on a sint~red glass filter funnel and dried in an oven a~ about 85C. An x-r~y diffraction pattern of the resulting dried product was obtained ~hich was almost identical ~ ~hat of LiMn204, but shifted to lower d-values. Table 1 presents the x-ray difraction pattern for the L~Mn204 prepared above, and the above ' dried, acid-treated product. Also presented ~n the Table for comparison are data from the ASTM card 18~736, for LiMn204 as compiled by the "American Society for Testing and Materials~" Ch~mical analysis, by conventional me~hods, o the acid-~reated produc~ indicated that ~he L~Mn204 had been converted to ~ubstantially pure MnO
The results of the chemical analysis are presented in Table 2.

_9 ` `i ~ ~3 113~8 ~ 345~5 o~CO `C; D ~a ~ C~
~ ~ _~
U~ _ ,.~
3i ~ :
~ o C: o ~:: o C
u~ u~ .~ ~ r~

H
_ ~
3 3 ~, ~ oc: o ~ o~:
E~ C1 ~, C~
C
Z ^ u~ I
C ~ Oc: O ~ oC ~ ~ ~cr~
~ _~ ~ U~ X
~ ~

Z ~o~ o C o<
Ooo ~ r~
.. ~ : ~ ~ r~

o -: o, E ~ ~ ,,~ ~ .
o~
`J `J
IY ~ ~ C~
p~
,_ _ I r~
r~ Oc~ o~ DI
~ `J ~
; , I V

va~ o~ 4 c v ~J o c t~ ~1 v ~ ~ ~ C O E~
c c a~ c u~ E 3 ~ C X

.
.

5~ 5 EXAMP$E II
Thls e~ample illus~rates a prefarred method of mak~ng L~Mn2O4 and al80 illustrates ~he u~e of different acids to convert L~Mn204 to the ~-MnO2 of this invention.

gms Li2CO3 and S00 ~ms Mn203 were ground ~oge her~ hea~ed in air at 850C for 1 hour; then cooled to room temperature, reground, then reheated at 8S0C ', for 1/2 hour.
Three 15 gm samples of the resulting LiMn2O4 were placed in beakers with 500 ml H20, and treated ~lth 3N HCl, 4.7N H2S04, and 4N HN03, respectively, to a pH
of sligh~ly balow 2. The samples were then wa~er washed until neutral, fil~ered and dried at~ 95C. X-ray results (Table 3~ and analytical results ~Table 4) confirm ~hat in all cases the LiMn2O~ was converted ~o substantially pure ~-M~O~--3 ~ ~ 3 ~ 5 o¢ o¢ o¢ o¢

r-i ~i~iL_i 3 ~ ~ ~
o¢ o¢ o¢ o¢ o c~ n ~n n r-i ~i~i r-i ~

~C ¢ ~ ¢ ~ cq 00 0~0~ co O
r-i r-i~i r~
~d S-a~
o ~i ¢ o¢ o<~ o¢ o¢
H 1~ r-i~I r-( ~ ri ~ O O O O ~rl ¢
K
~4 ~ '~
,_i o ¢ o ¢ o ¢
_~ ~rl S-l O O o U~ . . . b~
~-i C~ O
--i ~ri E~ 5~
U~ ri ~ri ~ æ
- ~i ~ ~
o¢ o~o ¢o ¢ O ~
~ æ ~ ~r-ic~i o Ç~i ~) ~ ~ ~ V.i ~
E¢-~ ~ iC~
. ~ P4 ~ ~
U~ o ¢
~i :~ ~ n "i i ~ o ¢ O¢ O¢ o¢ o¢

r-iC~i C~ i O
l ~ ~ ~ ~
. . . . ,~t; cq C~i C~C~l i tr - :~; a) i ~ ,t r~
¢
K v~ v.i vi v~ o 1:~ o ¢ o ¢ o ¢ o ¢ .LI ri H O~ C~i ~ ;;1- ~rl 1 1 1~ \~ ~ ~ 'd . . . . 'd O
:~ ~ ~ ~ ~ ~ ~
æ a) ~
'd rC
~ri H ~ ~d ~
O O O
~ O h ~1 5-1 ..
5~ r-i ~Q,O ,C4 ~ a) ~ æ~ci $: ~i O
td ,!~ q aJ ,!~ O O ~ri , Z
~X ~ J~ ~) 51 'd O ~-i - tl;- tli- t~i ~a~ o c~ ~i a)~c a~'d O V~
~ ri ri ~)ri ~ri ~J 11 11 11 ri 5~ 5~
~1 Q Q Q V~ E; 3 ~ ~ --12--~:
.

~.~.39L~5 113~8 o x o U~ U~ o~ ) I~
r~ r~ o~
P~
~;` ,~, ::
o~
~ ~ U~

,~ .

:

~: ~ ~ o r~ 03 ~o C ~

E~

ff Q~ U
~ ~ O :~
O X P~ O
C`~ W ~ ~4 ~ Q) ~ ~
O h ~ o h JJ
a~ o ~a ~ ~ ~ o U p.
-;t ~J O -O
ff ~ ~ 1 59 ~

113~8 EXAMPLE III
Thls example illu~trates the u8e of an elevated temperature aeid treatment. 60 gms Afr~ç~ MhO2 ore containing ~b~ut 74% MnO~ wa~ gr~und wi h 10.3 ~ms Li2C03, then heated at 850~C in air for 1 hour~ The sample ` was cooled 3 reground, then reheated ~t 850~C for 1 hour more~ The product showed the ~-ray pattern of Li~n20 and had 51.76% Mn, 57.04% MnO2, 70% peroxida~ion.
The analy ical re~ults indlcated that ~mpurities were present, carried over fr~m the ore.
Treating a 15 gm sample of the LiMn20~ product with H2S04 to a pH of 2 resulted in a product which had 75.82% MnO2, 92~/o peroxida~ion, and which showed the ~-MnO2 x ray pattern, indicating conversion to the new form of ~nO2O
However7 the low % MnO2 seen in the ~nalytical results indicated that the ore impurities remained high in the product.
A second 15 ~m sample of the Li2C03-treated ore wa~ acid ~reated, again to a pH of 2~ but this t~me the treating solutio~ was heated to 90C and maintained at that t~mperature for 30 minutes prior to washing with water. The resultant produet now ~ad 8403% M~02 and 97~/0 peroxidation snd still showed the~ ~MnO2 x-ray pattern.

~14-' ~ , 3 ~ ~ 5 11388 !

EXAMPLE IV
An 8.2 mg sample of A-MnO2 made according to ~he process described in Ex~mple II above, using H2S04, was placed on a porous nlckle subs~ra~e and discharged versus a 1ithium anode in ~n e1ectro1yte consistlng o lM
LiBF4 in 1:1 (volume ratio) propylene carbonate~
d~methoxyethane~ The current drain was 500 micro~mperes.
For comparison, a s~mllar æized (7~8 mg) sample of EMD
(electrolytic manganese dioxide)~ heat treated for 8 hours at 350-360C to opt~mize ~ts performance in the non-aqueous e1ectro1yte, was also discharged under ~he same condi~io~s.
The results re graphed in Figure 1; the horizonta1 a~is is e~pressed in a~pere-hours ~er gram, al~owing ~he nonmalization of the curves for differing sample ~eights.
The vertical axis shows the cell vol~ages during discharga.
The resu~ting discharge curves show that the ~-MnO~ has about the same total ampere-hour capac~ty as ~he EMD, but operates at a much higher volt~ge for ~he first half of the dischargeO
: A1though the present invention has been described nd ~e~ for~h in some de~ai1, i~ should be further understood tha~ the same is suscept1b1e to changes, modifications and variat1ons without departing fr~m the scope End spiri~ of the ~nven~ion.

Claims (13)

WHAT IS CLAIMED IS:
1. A manganese dioxide composition having the x-ray diffraction pattern:
dA
4.64 + 0.02 2.42 + 0.02 2.31 + 0.02 2.01 + 0.02 1.84 + 0.02 1.55 + 0.02 1.42 + 0.02?
2. The manganese dioxide of claim 1 wherein the relative intensities of the x-ray diffraction peaks are as follows:
dA Relative Intensity (Fe K? Radiation) 4.64 + 0.02 S
2.42 + 0.02 S
2.31 + 0.02 W
2.01 + 0.02 S
1.84 + 0.02 W
1.55 + 0.02 W
1.42 + 0.02 M
3. The manganese dioxide of claim 1 or 2 wherein the relative intensites of the x-ray diffraction peaks are as follows:

4. A method of manufacturing a manganese dioxide composition as defined in claim 1 comprising acid-treating LiMn2O4 with an aqueous acid solution until the pH of the solution stabilizes below about 2.5.
5. The method of claim 4 wherein the acid treatment comprises the steps of:
(a) suspending LiMn2O4 in water;
(b) adding aqueous acid while stirring;
(c) monitoring the pH of the solution phase;
and (d) continuing the acid addition until the pH of the solution phase stabilizes at below about pH 2.5.
6. The method of claim 5 comprising the additional steps of:
(e) washing until the wash water is about neutral;
(f) filtering; and (g) drying the MnO2 product.
7. The method of claims 5 or 6 wherein the acid addition step (d) is continued until the pH of the solution phase stabilizes at below about pH 2,0.
8. The method of claims 5 or 6 wherein the acid is selected from the group consisting of sulfuric acid, hydrochloric acid, and nitric acid,
9. The method of claim 4 wherein the manganese dioxide has the x-ray diffraction pattern:
dA
4.64 + 0.02 2.42 + 0.02 2.31 + 0.02 2.01 + 0.02 1.84 + 0.02 1.55 + 0.02 1.42 + 0.02
10. An electrochemical cell comprising an anode, a cathode, and an electrolyte, at least a portion of said cathode comprising .lambda.-MnO2.
11. The electrochemical cell of claim 10 wherein said electrolyte is selected from the group consisting of an aqueous electrolyte, a non-aqueous electrolyte, and a solid electrolyte.
12. The electrochemical cell of claim 11 wherein said non-aqueous electrolyte is 1 molar LiBF4 in 1:1 (volume ratio) propylene carbonate-di-methoxyethane.
13. The electrochemical cell of claim 12 wherein said anode is a Li anode.
CA000335495A 1978-09-29 1979-09-12 Mno.sub.2 derived from limn.sub.2o.sub.4 Expired CA1134595A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US947,120 1978-09-29
US05/947,120 US4246253A (en) 1978-09-29 1978-09-29 MnO2 derived from LiMn2 O4

Publications (1)

Publication Number Publication Date
CA1134595A true CA1134595A (en) 1982-11-02

Family

ID=25485548

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000335495A Expired CA1134595A (en) 1978-09-29 1979-09-12 Mno.sub.2 derived from limn.sub.2o.sub.4

Country Status (10)

Country Link
US (1) US4246253A (en)
EP (1) EP0009934B1 (en)
JP (1) JPS5834414B2 (en)
AU (1) AU5121879A (en)
BR (1) BR7906195A (en)
CA (1) CA1134595A (en)
DE (1) DE2963980D1 (en)
DK (1) DK408679A (en)
ES (2) ES8100225A1 (en)
NO (1) NO793102L (en)

Families Citing this family (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4304764A (en) * 1980-09-24 1981-12-08 Ray-O-Vac Corporation Protective active nitrides as additives to nonaqueous cathode materials
US4401737A (en) * 1980-09-24 1983-08-30 Rayovac Corporation Protective active nitrides as additives to nonaqueous cathode materials
US4507371A (en) * 1982-06-02 1985-03-26 South African Inventions Development Corporation Solid state cell wherein an anode, solid electrolyte and cathode each comprise a cubic-close-packed framework structure
JPS60189163A (en) * 1984-03-06 1985-09-26 Sony Corp Lithium-manganese dioxide battery
US4604336A (en) * 1984-06-29 1986-08-05 Union Carbide Corporation Manganese dioxide and process for the production thereof
GB2196785B (en) * 1986-10-29 1990-05-23 Sony Corp Organic electrolyte secondary cell
JPH0746607B2 (en) * 1987-01-29 1995-05-17 三洋電機株式会社 Non-aqueous secondary battery
JP2692932B2 (en) * 1989-02-20 1997-12-17 三洋電機株式会社 Non-aqueous secondary battery
GB2234233B (en) * 1989-07-28 1993-02-17 Csir Lithium manganese oxide
US5196279A (en) * 1991-01-28 1993-03-23 Bell Communications Research, Inc. Rechargeable battery including a Li1+x Mn2 O4 cathode and a carbon anode
US5135732A (en) * 1991-04-23 1992-08-04 Bell Communications Research, Inc. Method for preparation of LiMn2 O4 intercalation compounds and use thereof in secondary lithium batteries
FR2677636B1 (en) * 1991-06-17 1995-09-01 Technology Finance Corp MANGANESE DIOXIDE MATERIAL AND ELECTROCHEMICAL CELL CONTAINING THE SAME.
EP0581290B1 (en) * 1992-07-29 1999-07-07 Tosoh Corporation Novel manganese oxides, production thereof, and use thereof
JP3238954B2 (en) * 1992-09-25 2001-12-17 三洋電機株式会社 Non-aqueous secondary battery
DE69427692T2 (en) * 1993-04-06 2002-05-02 Ausmelt Ltd MELTING CARBON MATERIAL
US5425932A (en) * 1993-05-19 1995-06-20 Bell Communications Research, Inc. Method for synthesis of high capacity Lix Mn2 O4 secondary battery electrode compounds
CA2114493C (en) * 1994-01-28 1999-01-12 Jeffrey Raymond Dahn Method for increasing the reversible capacity of lithium transition metal oxide cathodes
US5820790A (en) * 1994-11-11 1998-10-13 Japan Storage Battery Co., Ltd. Positive electrode for non-aqueous cell
US6200542B1 (en) 1995-01-20 2001-03-13 Engelhard Corporation Method and apparatus for treating the atmosphere
US6863984B2 (en) 1995-01-20 2005-03-08 Engelhard Corporation Catalyst and adsorption compositions having improved adhesion characteristics
US20020018742A1 (en) * 1995-01-20 2002-02-14 Engelhard Corporation Method and apparatus for treating the atmosphere
US6517899B1 (en) 1995-01-20 2003-02-11 Engelhard Corporation Catalyst and adsorption compositions having adhesion characteristics
US20030166466A1 (en) * 1995-01-20 2003-09-04 Hoke Jeffrey B. Catalyst and adsorption compositions having improved adhesion characteristics
AU4701196A (en) 1995-01-20 1996-08-07 Engelhard Corporation Pollutant treating device located in vehicle compartment for cleaning ambient air
US6214303B1 (en) 1995-01-20 2001-04-10 Engelhard Corporation Method and apparatus for treating the atmosphere
US6818254B1 (en) * 1995-01-20 2004-11-16 Engelhard Corporation Stable slurries of catalytically active materials
US5693307A (en) * 1995-06-07 1997-12-02 Duracell, Inc. Process for making a lithiated lithium manganese oxide spinel
US5601796A (en) * 1995-11-22 1997-02-11 The Board Of Regents Of The University Of Oklahoma Method of making spinel LI2MN204 compound
US5792442A (en) * 1995-12-05 1998-08-11 Fmc Corporation Highly homogeneous spinel Li1+X Mn2-X O4 intercalation compounds and method for preparing same
WO1997037935A1 (en) * 1996-04-05 1997-10-16 Fmc Corporation METHOD FOR PREPARING SPINEL Li1+XMn2-XO4+Y INTERCALATION COMPOUNDS
US5770018A (en) * 1996-04-10 1998-06-23 Valence Technology, Inc. Method for preparing lithium manganese oxide compounds
US5976489A (en) * 1996-04-10 1999-11-02 Valence Technology, Inc. Method for preparing lithium manganese oxide compounds
US5670277A (en) * 1996-06-13 1997-09-23 Valence Technology, Inc. Lithium copper oxide cathode for lithium cells and batteries
US5744265A (en) * 1996-06-13 1998-04-28 Valence Technology, Inc. Lithium cell having mixed lithium--metal--chalcogenide cathode
US5718877A (en) * 1996-06-18 1998-02-17 Fmc Corporation Highly homogeneous spinal Li1+x Mn2-x O4+y intercalation compounds and method for preparing same
US5763120A (en) * 1996-06-25 1998-06-09 Valence Technology, Inc. Lithium manganese oxide cathodes with high capacity and stability
US5997831A (en) * 1996-07-12 1999-12-07 Engelhard Corporation Method of catalytically treating the atmosphere and heat exchange devices produced thereby
US5759510A (en) * 1996-10-03 1998-06-02 Carus Chemical Company Lithiated manganese oxide
US5824285A (en) * 1996-10-23 1998-10-20 Valence Technology, Inc. Method of making lithium manganese oxide compounds
US6156283A (en) * 1998-03-23 2000-12-05 Engelhard Corporation Hydrophobic catalytic materials and method of forming the same
US5955052A (en) 1998-05-21 1999-09-21 Carus Corporation Method for making lithiated manganese oxide
US5939043A (en) * 1998-06-26 1999-08-17 Ga-Tek Inc. Process for preparing Lix Mn2 O4 intercalation compounds
US6045950A (en) * 1998-06-26 2000-04-04 Duracell Inc. Solvent for electrolytic solutions
US6267943B1 (en) 1998-10-15 2001-07-31 Fmc Corporation Lithium manganese oxide spinel compound and method of preparing same
USH2121H1 (en) 2000-10-13 2005-08-02 The United States Of America As Represented By The Secretary Of The Navy High surface area, nanoscale, mesoporous manganese oxides with controlled solid-pore architectures and method for production thereof
US6645452B1 (en) 2000-11-28 2003-11-11 Valence Technology, Inc. Methods of making lithium metal cathode active materials
US6783893B2 (en) * 2001-11-19 2004-08-31 The Gillette Company Alkaline battery
US6759167B2 (en) * 2001-11-19 2004-07-06 The Gillette Company Primary lithium electrochemical cell
US7045252B2 (en) * 2002-08-08 2006-05-16 The Gillette Company Alkaline battery including lambda-manganese dioxide
US7585579B1 (en) 2003-07-29 2009-09-08 The United States Of America As Represented By The Secretary Of The Army Electrolyte for metal-oxygen battery and method for its preparation
US7147967B1 (en) 2003-07-29 2006-12-12 The United States Of America As Represented By The Secretary Of The Army Cathode for metal-oxygen battery
JP3742646B1 (en) * 2004-06-22 2006-02-08 三井金属鉱業株式会社 Cathode active material for lithium batteries
US7771873B2 (en) * 2005-07-12 2010-08-10 Panasonic Corporation Alkaline battery
US7718319B2 (en) * 2006-09-25 2010-05-18 Board Of Regents, The University Of Texas System Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries
CA2720600C (en) 2008-04-07 2017-09-12 Jay Whitacre Sodium ion based aqueous electrolyte electrochemical secondary energy storage device
US8142933B2 (en) * 2009-09-30 2012-03-27 Conocophillips Company Anode material for high power lithium ion batteries
US8303840B2 (en) * 2010-03-12 2012-11-06 The Gillette Company Acid-treated manganese dioxide and methods of making thereof
US20110223477A1 (en) * 2010-03-12 2011-09-15 Nelson Jennifer A Alkaline battery including lambda-manganese dioxide and method of making thereof
US8298706B2 (en) 2010-03-12 2012-10-30 The Gillette Company Primary alkaline battery
US20110219607A1 (en) * 2010-03-12 2011-09-15 Nanjundaswamy Kirakodu S Cathode active materials and method of making thereof
WO2012148569A2 (en) 2011-03-01 2012-11-01 Aquion Energy Inc. Profile responsive electrode ensemble
US8298701B2 (en) 2011-03-09 2012-10-30 Aquion Energy Inc. Aqueous electrolyte energy storage device
US8137830B2 (en) 2011-07-19 2012-03-20 Aquion Energy, Inc. High voltage battery composed of anode limited electrochemical cells
US8945751B2 (en) 2011-07-19 2015-02-03 Aquion Energy, Inc. High voltage battery composed of anode limited electrochemical cells
US8652672B2 (en) 2012-03-15 2014-02-18 Aquion Energy, Inc. Large format electrochemical energy storage device housing and module
US9570741B2 (en) 2012-03-21 2017-02-14 Duracell U.S. Operations, Inc. Metal-doped nickel oxide active materials
US8703336B2 (en) 2012-03-21 2014-04-22 The Gillette Company Metal-doped nickel oxide active materials
US9028564B2 (en) 2012-03-21 2015-05-12 The Gillette Company Methods of making metal-doped nickel oxide active materials
GB2503896A (en) 2012-07-10 2014-01-15 Faradion Ltd Nickel doped compound for use as an electrode material in energy storage devices
GB2503898A (en) 2012-07-10 2014-01-15 Faradion Ltd Nickel doped compound for use as an electrode material in energy storage devices
GB2506859A (en) 2012-10-09 2014-04-16 Faradion Ltd A nickel-containing mixed metal oxide active electrode material
GB201221425D0 (en) 2012-11-28 2013-01-09 Faradion Ltd Metal-containing compound
US8945756B2 (en) 2012-12-12 2015-02-03 Aquion Energy Inc. Composite anode structure for aqueous electrolyte energy storage and device containing same
GB201223473D0 (en) 2012-12-28 2013-02-13 Faradion Ltd Metal-containing compounds
GB201308654D0 (en) 2013-05-14 2013-06-26 Faradion Ltd Metal-containing compounds
KR102196363B1 (en) * 2013-10-29 2020-12-30 삼성전자주식회사 Electrode active material for magnesium battery, electrode and magnesium battery comprising the same, and electrode active material preparation method for magnesium battery
US9793542B2 (en) 2014-03-28 2017-10-17 Duracell U.S. Operations, Inc. Beta-delithiated layered nickel oxide electrochemically active cathode material and a battery including said material
US10804536B2 (en) 2017-02-13 2020-10-13 Energizer Brands, Llc Substituted lambda manganese dioxides in an alkaline electrochemical cell
EP3848330A1 (en) 2017-05-09 2021-07-14 Duracell U.S. Operations, Inc. Battery including beta-delithiated layered nickel oxide electrochemically active cathode material
US11133499B2 (en) 2019-05-16 2021-09-28 Energizer Brands, Llc Substituted ramsdellite manganese dioxides in an alkaline electrochemical cell
WO2021080548A1 (en) 2019-10-21 2021-04-29 Zurab Davidovych Gogitidze A cathode material

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA714989A (en) * 1965-08-03 Mehne Artur Process for finishing artificial pyrolusite
US1988799A (en) * 1929-02-25 1935-01-22 Kaoru Oyama Manufacture of manganese dioxide
BE500599A (en) * 1950-01-16
DE1152095B (en) * 1959-08-12 1963-08-01 Knapsack Ag Process for the production of artificial brown stone of the ªÃ "modification
DE1189960B (en) * 1962-10-27 1965-04-01 Varta Pertrix Union Ges Mit Be Process for the production of ramsdellite
FR1443907A (en) * 1965-01-21 1966-07-01 New manganese dioxide, its preparation process and its applications
BE757890A (en) * 1969-10-22 1971-04-01 Japan Metals And Chemicals Cy MANGANESE BIOXIDE PRODUCTION PROCESS
US3959021A (en) * 1969-12-29 1976-05-25 Matsushita Electric Industrial Co., Ltd. Novel manganese dioxide
US3856576A (en) * 1973-06-25 1974-12-24 Kerr Mc Gee Chem Corp Process of treating electrolytic manganese dioxide
JPS5124999A (en) * 1974-08-23 1976-02-28 Sakae Fujiwara JIDODABUTEERUKATSUTAAKUDOSOCHI

Also Published As

Publication number Publication date
ES484508A0 (en) 1980-11-01
DE2963980D1 (en) 1982-12-09
NO793102L (en) 1980-04-01
BR7906195A (en) 1980-09-09
ES8100225A1 (en) 1980-11-01
AU5121879A (en) 1980-04-03
ES8202188A1 (en) 1981-09-01
US4246253A (en) 1981-01-20
JPS55100224A (en) 1980-07-31
DK408679A (en) 1980-03-30
EP0009934B1 (en) 1982-11-03
JPS5834414B2 (en) 1983-07-26
ES491736A0 (en) 1981-09-01
EP0009934A1 (en) 1980-04-16

Similar Documents

Publication Publication Date Title
CA1134595A (en) Mno.sub.2 derived from limn.sub.2o.sub.4
US4312930A (en) MnO2 Derived from LiMn2 O4
DE69124158T3 (en) Lithium-containing nickel dioxide and galvanic secondary elements made from it
Thackeray et al. Electrochemical extraction of lithium from LiMn2O4
Bach et al. Birnessite manganese dioxide synthesized via a sol—gel process: a new rechargeable cathodic material for lithium batteries
US6680143B2 (en) Lithium metal oxide electrodes for lithium cells and batteries
US4604336A (en) Manganese dioxide and process for the production thereof
DE69705039T2 (en) METHOD FOR PRODUCING A LITHIUM MANGANOXIDE SPINEL
US6190800B1 (en) Lithiated manganese dioxide
US4585718A (en) Lithium-manganese dioxide cell
DE69518719T2 (en) Positive active electrode material for non-aqueous cell and manufacturing process
US4476104A (en) Manganese dioxide and process for the production thereof
Wu et al. Preparation and electrochemical performance of Li-rich layered cathode material, Li [Ni0. 2Li0. 2Mn0. 6] O2, for lithium-ion batteries
EP0624552B1 (en) Novel method for preparing solid solution materials for secondary non-aqueous batteries
Kijima et al. Lithium ion insertion and extraction reactions with Hollandite-type manganese dioxide free from any stabilizing cations in its tunnel cavity
DE19751552C2 (en) Active material for the cathode of a lithium ion battery and method of manufacture
DE112018000205T5 (en) A METHOD FOR PRODUCING A POWERFUL LITHIUM TITANATE ANODE MATERIAL FOR APPLICATIONS OF LITHIUM-ION ACCUMULATORS
Ostafiychuk et al. Synthesis and electrochemical properties of LaMnO3 perovskite nanoparticles
Saidi et al. Structural and electrochemical investigation of lithium insertion in the Li1− xMn2O4 spinel phase
US5747193A (en) Process for synthesizing lixmny04 intercalation compounds
KR102726394B1 (en) Preparation method of ceria nanoparticles doped with metal using ultrasonic waves
Davies et al. Sol–gel-derived vanadium and titanium oxides as cathode materials in high-temperature lithium polymer-electrolyte cells
US5961950A (en) Method for preparing solid solution materials such as lithium manganese oxide
DE69726351T2 (en) Lithium iron oxide and process for its manufacture
JP7377518B2 (en) Electrode materials and electrodes and batteries using the same

Legal Events

Date Code Title Description
MKEX Expiry
MKEX Expiry

Effective date: 19991102